CN107108549A

CN107108549A - Compound, resin, photoetching substrate film formation material, photoetching basilar memebrane, pattern formation method and purification process

Info

Publication number: CN107108549A
Application number: CN201580070416.3A
Authority: CN
Inventors: 樋田匠; 越后雅敏; 佐藤隆; 牧野岛高史
Original assignee: Mitsubishi Gas Chemical Co Inc
Current assignee: Mitsubishi Gas Chemical Co Inc
Priority date: 2014-12-25
Filing date: 2015-12-14
Publication date: 2017-08-29
Also published as: IL253109A0; EP3239141A4; EP3239141A1; US20170349564A1; TW201629031A; WO2016104214A1; SG11201705038XA; KR20170099908A; JPWO2016104214A1; JP7026439B2; US10745372B2

Abstract

A kind of compound shown in following formula (1).(in formula (1), X separately represents oxygen atom or sulphur atom or for without crosslinking, R¹For singly-bound or the 2n valency groups of carbon number 1~30, the group optionally has the aryl of alicyclic type hydrocarbon, double bond, hetero atom or carbon number 6~30, R²It is separately the straight-chain of carbon number 1~10, the alkyl of branched or ring-type, the aryl of carbon number 6~10, the alkenyl of carbon number 2~10, the alkoxy of carbon number 1~30, the aryloxy group or hydroxyl of carbon number 6~30, herein, R²In at least one for carbon number 1~30 alkoxy or carbon number 6~30 aryloxy group, m separately be 1~6 integer, the integer that p is separately 0 or 1, n are 1~4.)

Description

Compound, resin, photoetching substrate film formation material, photoetching basilar memebrane, pattern shape Into method and purification process

Technical field

The present invention relates to compound, resin, photoetching substrate film formation material, photoetching basilar memebrane, pattern formation method And purification process.

Background technology

In the manufacture of semiconductor devices, the microfabrication based on the photoetching using photo anti-corrosion agent material has been carried out, but Recently as LSI highly integrated and high speed, it is desirable to based on the further miniaturization of pattern rule.Using being used as In the photoetching of the light exposure of current general technology, the boundary of the resolution ratio of the wavelength from light source in itself is just being moved closer to.

The light source of the photoetching used during corrosion-resisting pattern formation is to be turned to by KrF PRKs (248nm) by short wavelength ArF PRKs (193nm).However, during the development of corrosion-resisting pattern miniaturization, the problem of resolution ratio can be produced or in development The problem of corrosion-resisting pattern collapses afterwards, it is therefore desirable for the filming of resist.For such urgent expectation, if only carrying out resist Filming, then become to be difficult to the corrosion-resisting pattern thickness for obtaining being sufficient for substrate processing.Therefore, not only corrosion-resisting pattern needs, Resist-based counterdie is made between resist and the semiconductor substrate processed, is also required to make it for the resist-based counterdie With the technique when substrate is processed as mask functions.

Now, as the resist-based counterdie of such technique, it is known to various resist-based counterdies.For example, can be with Enumerate different from the resist-based counterdie that conventional etching speed is fast, with the dry etching rate selection ratio close with resist Photoetching resist-based counterdie.It is used as the material for forming such photoetching resist-based counterdie, it is proposed that a kind of multilayer Resist technique substrate film formation material, it contains resin component and solvent, and the resin component at least has by applying Defined energy and depart from terminal groups to produce the substituents of sulfonic acid moieties (referring for example to patent document 1).Furthermore it is possible to Enumerate the photoetching resist-based counterdie that ratio is selected with the dry etching rate smaller than resist.As for forming such light Carve the material with resist-based counterdie, it is proposed that the resist-based base film material containing the polymer with specific repeat unit (referring for example to patent document 2).And then, the photoetching with the dry etching rate selection ratio smaller than semiconductor substrate can be enumerated and used Resist-based counterdie.It is used as the material for forming such photoetching resist-based counterdie, it is proposed that containing making acenaphthylene class Repeat unit carries out the resist-based counterdie of the polymer of copolymerization with the repeat unit with substituted or unsubstituted hydroxyl Material (referring for example to patent document 3).

On the other hand, as the material in this resist-based counterdie with high elching resistant, it is well known that logical Cross and used amorphous carbon basilar memebrane formed by the CVD of methane gas, ethane gas, acetylene gas etc. in the feed.However, From technologic viewpoint, it is desirable to resist-based bottom can be formed by wet processings such as method of spin coating, silk-screen printings The resist-based base film material of film.

In addition, the present inventor etc. proposes following photoetching basilar memebrane formation composition, wherein, as optical characteristics and Elching resistant is excellent, while dissolving in solvent and can apply the material of wet processing, contains the naphthalene comprising specific structure unit Yuban and organic solvent (referring for example to patent document 4 and 5).

It should be noted that in 3 layer process formed resist-based counterdie when used intermediate layer forming method, It is for example known to there is the forming method (referring for example to patent document 6) of silicon nitride film, the CVD forming methods of silicon nitride film (such as to join According to patent document 7).In addition, being used as the intermediate layer material of 3 layer process, it is known to which the silication comprising silsesquioxane basis is closed The material of thing (referring for example to patent document 8 and 9).

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2004-177668 publications

Patent document 2：Japanese Unexamined Patent Publication 2004-271838 publications

Patent document 3：Japanese Unexamined Patent Publication 2005-250434 publications

Patent document 4：International Publication No. 2009/072465

Patent document 5：International Publication No. 2011/034062

Patent document 6：Japanese Unexamined Patent Publication 2002-334869 publications

Patent document 7：International Publication No. 2004/066377

Patent document 8：Japanese Unexamined Patent Publication 2007-226170 publications

Patent document 9：Japanese Unexamined Patent Publication 2007-226204 publications

The content of the invention

Problems to be solved by the invention

As described above, a variety of photoetching substrate film formation materials were proposed in the past, but requiring not only to have to apply The solvent solubility of the wet processings such as method of spin coating, silk-screen printing, but also heat resistance and elching resistant are had concurrently with high level, And to for making the deliquescent further improvement of the highly stable safety solvent of product property.

The present invention be in view of above-mentioned problem and make, its object is to there is provided：In order to form photoresist basilar memebrane And it is useful, can be using wet processing, heat resistance and elching resistant is excellent and dissolubility of to safety solvent is further obtained Improved compound and resin, substrate film formation material and pattern formation method.

The solution used to solve the problem

The present inventor etc. further investigate repeatedly in order to solve above-mentioned problem, as a result find：By using with specific structure Compound or resin, so as to solve above-mentioned problem, so far complete the present invention.

I.e., the present invention provides following [1]~[19].

[1]

A kind of compound shown in following formula (1).

(in formula (1), X separately represents oxygen atom or sulphur atom or for without crosslinking, R¹For singly-bound or carbon number 1~ 30 2n valency groups, the group optionally has the aryl of alicyclic type hydrocarbon, double bond, hetero atom or carbon number 6~30, R²Independently Ground is the straight-chain of carbon number 1~10, the alkyl of branched or ring-type, the aryl of carbon number 6~10, the alkenyl of carbon number 2~10, carbon The alkoxy of number 1~30, the aryloxy group or hydroxyl of carbon number 6~30, herein, R²In at least one be carbon number 1~30 alkoxy Or the aryloxy group of carbon number 6~30, m is separately 1~6 integer, the integer that p is separately 0 or 1, n are 1~4.)

[2]

Compound according to [1], wherein, the compound shown in previously described formula (1) is the change shown in following formula (1A-2) Compound.

(in formula (1A-2), R¹With p implication, R as hereinbefore⁶With the R of explanation in previously described formula (1)²For identical meanings, m⁶Point 1~3 integer independently is not.)

[3]

Compound according to [1], wherein, the compound shown in previously described formula (1) is the change shown in following formula (1B-2) Compound.

(in formula (1B-2), R¹With p and foregoing same, R⁶With the R of explanation in previously described formula (1)²For identical meanings, m⁶It is only respectively On the spot be 1~3 integer.)

[4]

Compound according to [2], wherein, the compound shown in previously described formula (1A-2) is following formula (BisN-1-CH1) Or the compound shown in following formula (BisN-1-CH2).

[5]

Compound according to [2], wherein, the compound shown in previously described formula (1A-2) is following formula (BisN-1-PH1) Or the compound shown in following formula (BisN-1-PH2).

[6]

A kind of resin, its be using the compound any one of [1]~[5] as obtained from monomer.

[7]

Resin according to [6], it is with having cross-linking reaction by the compound any one of [1]~[5] Property compound reaction obtained from.

[8]

Resin according to [7], wherein, the compound with crosslinking reactivity be selected from by aldehyde, ketone, carboxylic acid, Acid halide, halogen contained compound, amino-compound, imino-compound, isocyanates and the compound group containing unsaturated alkyl Into group in it is at least one kind of.

[9]

Resin according to [6] is comprising structure shown in following formula (2).

(in formula (2), X separately represents oxygen atom or sulphur atom or for without crosslinking, R¹For singly-bound or carbon number 1~ 30 2n valency groups, the group optionally has the aryl of alicyclic type hydrocarbon, double bond, hetero atom or carbon number 6~30, R²Independently Ground is the straight-chain of carbon number 1~10, the alkyl of branched or ring-type, the aryl of carbon number 6~10, the alkenyl of carbon number 2~10, carbon The alkoxy of number 1~30, the aryloxy group or hydroxyl of carbon number 6~30, herein, R²In at least one be carbon number 1~30 alkoxy Or the aryloxy group of carbon number 6~30, R³It is separately the straight-chain or the alkylidene of branched of singly-bound or carbon number 1~20, m² Separately be 1~5 integer, the integer that p is separately 0 or 1, n are 1~4.)

[10]

Resin according to [9], wherein, the resin with the structure shown in previously described formula (2) is with following formula (2A) The resin of shown structure.

(in formula (2A), R¹、R²、R³、m², p and n with it is foregoing same.)

[11]

Resin according to [9], wherein, the resin with the structure shown in previously described formula (2) is with following formula (2B) The resin of shown structure.

(in formula (2B), R¹、R²、R³、m², p and n with it is foregoing same.)

[12]

A kind of photoetching substrate film formation material, it contains：[1] compound and/or [6] any one of~[5] Resin any one of~[11].

[13]

Photoetching according to [12] substrate film formation material, wherein, also contain organic solvent.

[14]

Photoetching substrate film formation material according to [12] or [13], wherein, also contain acid agent.

[15]

Photoetching substrate film formation material according to any one of [12]~[14], wherein, also contain crosslinking agent.

[16]

A kind of photoetching basilar memebrane, it is as the substrate film formation material shape of the photoetching any one of [12]~[15] Into.

[17]

A kind of corrosion-resisting pattern forming method, it possesses following process：

Process (A-1), uses the photoetching substrate film formation material any one of [12]~[15], the shape on substrate Into basilar memebrane；

Process (A-2), forms at least 1 layer of photoresist layer on aforementioned substrates film；With,

Process (A-3), after foregoing sequence (A-2), to the predetermined region illumination radiation line of foregoing photoresist layer, enters Row development.

[18]

A kind of circuit pattern forming method, it possesses following process：

Process (B-1), uses the photoetching substrate film formation material any one of [12]~[15], the shape on substrate Into basilar memebrane；

Process (B-2), using the resist interlayer film material containing silicon atom, intermediate layer is formed on aforementioned substrates film Film；

Process (B-3), in the preamble between at least 1 layer of photoresist layer is formed on tunic；

Process (B-4), after foregoing sequence (B-3), to the predetermined region illumination radiation line of foregoing photoresist layer, enters Row develops and forms corrosion-resisting pattern；With,

Process (B-5), after foregoing sequence (B-4), using the corrosion-resisting pattern as mask, loses to foregoing interlayer film Carve, using gained interlayer film pattern as etching mask, aforementioned substrates film is etched, covered using gained substrate film figure as etching Mould, is etched to substrate, so as to form pattern on substrate.

[19]

A kind of purification process, it includes the process for making solution (A) contact to be extracted with acidic aqueous solution, the solution (A) contain：Compound or [6]~[11] any one of the organic solvent not mixed arbitrarily with water and [1]~[5] Any one of resin.

The effect of invention

According to the present invention it is possible to realize in order to form photoresist basilar memebrane and it is useful, can using wet processing, Heat resistance and elching resistant is excellent and dissolubility of to safety solvent is further improved compound, resin and photoetching are used Substrate film formation material.

Embodiment

Hereinafter, embodiments of the present invention (hereinafter referred to as present embodiment) are illustrated.It should be noted that this Embodiment is the example for illustrating the present invention, and the present invention is not limited to present embodiment.

[compound]

Shown in the compound of present embodiment such as following formula (1).

Due to said structure, therefore, the compound of present embodiment in order to form photoresist basilar memebrane but Useful, wet processing can be applied, heat resistance and elching resistant are excellent, and the dissolubility of safety solvent is further changed It is kind.It should be noted that the compound of present embodiment due to the feature in its structure it may be said that heat resistance is high, concentration of carbon compared with High, oxygen concentration is relatively low, solvent solubility is also high.Photoetching basilar memebrane shape is used as using the compound with such regulation structure In the case of material, the deterioration that can form film when high temperature is bakeed is suppressed, to the anti-corrosion of oxygen gas plasma etching etc. Quarter property also excellent basilar memebrane, and then, the adaptation with resist layer is also excellent, therefore, it can obtain excellent corrosion-resisting pattern.

In above-mentioned formula (1), X separately represents oxygen atom or sulphur atom or for without crosslinking.Herein, X is without crosslinking When, it is the compound shown in following formula (1B) to refer to the compound shown in formula (1).

(in formula (1B), R¹、R², m, p and n with it is foregoing same.)

Above-mentioned R¹For singly-bound or the 2n valency groups of carbon number 1~30.The compound of present embodiment has by R¹Connect each benzene The composition of ring.Herein, 2n valencys group optionally has the aryl of alicyclic type hydrocarbon, double bond, hetero atom or carbon number 6~30.

Above-mentioned R²It is separately the alkyl selected from straight-chain, branched or ring-type by carbon number 1~10, carbon number 6 The group that~10 aryl, the alkenyl of carbon number 2~10, the alkoxy of carbon number 1~30, the aryloxy group of carbon number 6~30 and hydroxyl is constituted In 1 valency group, each m are connected on each aromatic rings.Herein, R²In at least one be carbon number 1~30 alkoxy or carbon number 6 ~30 aryloxy group.

In addition, m is separately 1~6 integer.P is separately 0 or 1.N is 1~4 integer.

For the group of foregoing 2n valencys, in n=1, the alkylidene of carbon number 1~30 is represented, in n=2, carbon number 1 is represented ~30 base of alkane four, in n=3, represents the base of alkane six of carbon number 2~30, in n=4, represents the alkane of carbon number 3~30 Eight bases.As the group of foregoing 2n valencys, for example, it can enumerate the group with straight-chain, branched or cyclic structure.

In addition, foregoing 2n valencys group optionally has the aryl of alicyclic type hydrocarbon, double bond, hetero atom or carbon number 6~30.This Place, for foregoing alicyclic type hydrocarbon, also comprising bridging alicyclic type hydrocarbon.

And then, the alkoxy of carbon number 1~30 is following group：It is by selected from by straight-chain alkyl, branched alkyl, alicyclic ring Group and oxygen atom in the group that formula alkyl, aromatic hydrocarbyl and the combination of their more than two are formed are constituted.Herein, For foregoing alicyclic type hydrocarbon, also comprising bridging alicyclic type hydrocarbon.In addition, the alkoxy optionally has double bond, hetero atom, halogen former Son.

As the alkoxy of carbon number 1~30, it is not particularly limited, preferably enumerates：Methoxyl group, ethyoxyl, propoxyl group, fourth oxygen Base, amoxy, hexyloxy, cyclobutoxy group, cyclopentyloxy, cyclohexyloxy, cyclohexenyl group epoxide, isophorone base epoxide, drop ice Piece alkyl oxy, adamantyl epoxide, tricyclodecyl epoxide, pyridine radicals epoxide, phenyl epoxide, aminomethyl phenyl epoxide, dimethyl Phenyl epoxide, ethylphenyl epoxide, fluorophenyl epoxide, chlorphenyl epoxide, bromophenyl epoxide, iodophenyl epoxide, hydroxy phenyl oxygen Base, methoxyphenyl epoxide, aminophenyl epoxide, nitrobenzophenone epoxide, cyano-phenyl epoxide, phenyl epoxide, phenyl oxygen Base phenyl epoxide, naphthyl epoxide, methyl naphthyl epoxide, dimethyl naphthyl epoxide, ethyl naphthyl epoxide, fluoronaphthalene base epoxide, chloronaphthalene Base epoxide, bromonaphthalene base epoxide, iodine naphthyl epoxide, hydroxynaphenyl epoxide, methoxyl group naphthyl epoxide, amino naphthyl epoxide, nitronaphthalene Base epoxide, cyanonaphthyl epoxide, phenyl napthyl epoxide, phenyl epoxide naphthyl epoxide, anthryl epoxide, pyrenyl epoxide, fluorenyl epoxide, More preferably enumerate：Cyclobutoxy group, cyclopentyloxy, cyclohexyloxy, cyclohexenyl group epoxide, isophorone base epoxide, norborneol alkyl Epoxide, adamantyl epoxide, tricyclodecyl epoxide, pyridine radicals epoxide, phenyl epoxide, aminomethyl phenyl epoxide, 3,5-dimethylphenyl oxygen Base, ethylphenyl epoxide, fluorophenyl epoxide, chlorphenyl epoxide, bromophenyl epoxide, iodophenyl epoxide, hydroxy phenyl epoxide, methoxy Base phenyl epoxide, aminophenyl epoxide, nitrobenzophenone epoxide, cyano-phenyl epoxide, phenyl epoxide, phenyl phenyl oxygen Base, naphthyl epoxide, methyl naphthyl epoxide, dimethyl naphthyl epoxide, ethyl naphthyl epoxide, fluoronaphthalene base epoxide, chloronaphthyl, methylnaphthyl epoxide, bromine Naphthyl epoxide, iodine naphthyl epoxide, hydroxynaphenyl epoxide, methoxyl group naphthyl epoxide, amino naphthyl epoxide, nitro naphthyl epoxide, cyanogen Base naphthyl epoxide, phenyl napthyl epoxide, phenyl epoxide naphthyl epoxide, anthryl epoxide, pyrenyl epoxide, fluorenyl epoxide, it is further excellent Elect：Cyclobutoxy group, cyclopentyloxy, cyclohexyloxy, cyclohexenyl group epoxide, isophorone base epoxide, norborneol alkyl oxy, Adamantyl epoxide, tricyclodecyl epoxide, pyridine radicals epoxide, phenyl epoxide, aminomethyl phenyl epoxide, 3,5-dimethylphenyl epoxide, second Base phenyl epoxide, methoxyphenyl epoxide, phenyl epoxide, phenyl phenyl epoxide, naphthyl epoxide, methyl naphthyl oxygen Base, dimethyl naphthyl epoxide, ethyl naphthyl epoxide, methoxyl group naphthyl epoxide, phenyl napthyl epoxide, phenyl epoxide naphthyl epoxide, Anthryl epoxide, pyrenyl epoxide, fluorenyl epoxide, are particularly preferably enumerated：Cyclohexyloxy, phenyl epoxide.

The aryloxy group of carbon number 6~30 is the group being made up of the aromatic hydrocarbyl of carbon number 6~30 with oxygen atom, is conducive to carrying The dissolubility of compound shown in high formula (1).As the concrete example of the aryloxy group of such carbon number 6~30, be not limited to it is following, It can enumerate：Phenyl epoxide, aminomethyl phenyl epoxide, 3,5-dimethylphenyl epoxide, trimethylphenyl epoxide, ethylphenyl epoxide, third Base phenyl epoxide, butyl phenyl epoxide, cyclohexyl phenyl epoxide, xenyl epoxide, terphenyl epoxide, naphthyl epoxide, fluorenyl Epoxide, anthryl epoxide, pyrenyl epoxide, methyl pyrenyl epoxide, dimethyl pyrenyl epoxide etc..

Compound shown in previously described formula (1) is not only lower molecular weight, and is had more using the outspoken nature of its structure High heat resistance, therefore can also be used under high temperature baking conditions.Further, since for lower molecular weight and low viscosity, therefore, Even if being the substrate (particularly fine area, sectional hole patterns etc.) with difference in height, also easily fill uniformly with to the difference in height Everywhere, embedment characteristic and planarization characteristics are advantageously improved as a result, having using its photoetching substrate film formation material Tendency.Further, since being the compound with higher carbon concentration, accordingly it is also possible to assign high elching resistant.And then, pass through Alkoxy with carbon number 1~30, to for making the dissolubility of the highly stable safety solvent of product property further be changed It is kind.

Herein, the aspect improved from the heat resistance formed based on upright and outspoken structure, the compound shown in previously described formula (1) is excellent Elect the compound shown in following formula (1A) as.

In previously described formula (1A), R¹、R², m, p and n with it is foregoing same.

In addition, from improving the deliquescent aspect of safety solvent, the compound shown in previously described formula (1) is preferably following formula Compound shown in (1B).

In previously described formula (1B), R¹、R², m, p and n with it is foregoing same.

From importing R⁵O groups and the degree of cross linking during baking produced improve the aspect that caused heat resistance improves and set out, Compound shown in previously described formula (1A) is more preferably the compound shown in formula (1A-1).

(in formula (1A-1), R⁴It is separately the straight-chain of carbon number 1~10, the alkyl of branched or ring-type, carbon number 6~10 aryl, the alkenyl or hydroxyl of carbon number 2~10, R⁵For 1 valency group of carbon number 1~30, for selected from by straight-chain alkyl, Group in the 1 valency group that branched alkyl, alicyclic type hydrocarbon, aromatic hydrocarbyl and the combination of their more than two are formed. The group optionally has double bond, hetero atom, halogen atom.Herein, for foregoing alicyclic type hydrocarbon, also comprising bridging ester ring type hydrocarbon Base.m₃Separately be 0~4 integer, herein, at least one m₃For 1, m₄Separately be 0~3 integer, m₃+m₄For 1 ~4 integer, R¹, n and p with it is foregoing same.)

From importing R⁵The further deliquescent aspect of raising safety solvent produced by O bases is set out, shown in previously described formula (1B) Compound be more preferably compound shown in formula (1B-1).

(in formula (1B-1), R¹、R⁴、R⁵、m₃、m₄, n and p with it is foregoing same.)

In addition, from the viewpoint of for low molecule amount, it in formula (1) is n=1 that the compound shown in previously described formula (1), which is preferably, Scheme, i.e. following formula (1-2) shown in compound.

In previously described formula (1-2), X, R¹With p with illustrating in previously described formula (1) for identical meanings, R⁶With explanation in previously described formula (1) R²For identical meanings, m⁶For 1~3 integer.

In addition, from the viewpoint of the heat resistance formed based on upright and outspoken structure is improved, the compound shown in previously described formula (1-2) It is the compound shown in X=O scheme, i.e. following formula (1A-2) more preferably in previously described formula (1-2).

In previously described formula (1A-2), R¹With p with illustrating in previously described formula (1) for identical meanings.R⁶With explanation in previously described formula (1) R²For identical meanings, m⁶For 1~3 integer.

In addition, from the viewpoint of safety solvent dissolubility is improved, before the compound shown in previously described formula (1-2) is more preferably It is the compound shown in the scheme without crosslinking, i.e. following formula (1B-2) to state X in formula (1-2).

In previously described formula (1B-2), R¹With p with illustrating in previously described formula (1) for identical meanings.R⁶With explanation in previously described formula (1) R²For identical meanings, m⁶For 1~3 integer.

From the viewpoint of solubility and heat resistance is had concurrently, the compound shown in above-mentioned formula (1A-2) is preferably following formula Compound shown in (1A-3).

In previously described formula (1A-3), R¹With illustrating in previously described formula (1) for identical meanings, R⁵With explanation in previously described formula (1A-1) For identical meanings.

From the viewpoint of solubility and heat resistance is had concurrently, the compound shown in above-mentioned formula (1B-2) is preferably following formula Compound shown in (1B-3).

In previously described formula (1B-3), R¹With illustrating in previously described formula (1) for identical meanings, R⁵With explanation in previously described formula (1A-1) For identical meanings.

The concrete example of compound shown in the example below previously described formula (1), but be not limited to enumerate herein.

In previously described formula, R², X and m and explanation in above-mentioned formula (1) be identical meanings.

The concrete example of compound shown in example previously described formula (1), but be not limited to enumerate herein further below.

In previously described formula, X in previously described formula (1) with illustrating for identical meanings, R⁵With illustrating in previously described formula (1A-1) for phase Same implication.

In addition, from the viewpoint of dissolubility, the compound shown in previously described formula (1A-2) is particularly preferably following formula Or the compound shown in following formula (BisN-1-CH2) (BisN-1-CH1).

In addition, from the viewpoint of dissolubility, the compound shown in previously described formula (1A-2) is also preferably following formula (BisN- 1-PH1) or the compound shown in following formula (BisN-1-PH2).

Compound shown in previously described formula (1) can suitably be synthesized using known method, to its synthetic method without spy Do not limit.For example, at ambient pressure, under an acid catalysis, make corresponding with the structure of desired compound phenols or thiophenols, Corresponding with the structure of desired compound aldehydes or ketone carry out polycondensation reaction, so as to obtain previously described formula (1) institute The compound shown.In addition, as needed, can also carry out under elevated pressure.By changing reaction condition, it can control to be crosslinked with X When structure when being without crosslinking of structure and X generation ratio.For example, improving reaction temperature or extension reaction time or increasing During the acid strength of strong acid catalyst, have the tendency of to uprise with the generation ratio of the X structures being crosslinked.On the other hand, reduction reaction During the acid strength of temperature or shortening reaction time or decrease acid catalyst, there is the generation ratio using X as the structure without crosslinking to become High tendency.When paying attention to high solvent dissolubility, the ratio of structure when preferably X is without crosslinking is high, and payes attention to high-fire resistance When, the ratio of structure when being preferably crosslinked with X is high.

As foregoing phenolic, for example, it can enumerate：Phenol, methylphenol, methoxybenzene, catechol, resorcinol, hydrogen Quinone etc., but it is not particularly limited in these.They can be used alone, or combine two or more and use.Wherein, from can be easy Set out in terms of forming xanthene structure, more preferably using quinhydrones.

As foregoing thiophenols, for example, it can enumerate：Benzenethiol, methylbenzenethiol, methoxybenzene thiol, dimercaptobenzene Deng, but it is not particularly limited in these.They can be used alone, or combine two or more and use.Wherein, from being capable of easy shape Into setting out in terms of thioxanthene structure, it is more suitable for using dimercaptobenzene.

As foregoing aldehydes, for example, it can enumerate：Formaldehyde, metaformaldehyde, paraformaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, hexanal, Capraldehyde, the hendecanal, phenylacetaldehyde, benzenpropanal, furfural, benzaldehyde, hydroxy benzaldehyde, fluorobenzaldehyde, chlorobenzaldehyde, nitrobenzoyl Aldehyde, tolyl aldehyde, dimethylbenzaldehyde, ethylo benzene formaldehyde, propylbenzaldehyde, butyl benzaldehyde, cyclohexyl benzene formaldehyde, biphenyl Formaldehyde, naphthaldehyde, anthraldehyde, formaldehyde, pyrene formaldehyde, glyoxal, glutaraldehyde, OPA, naphthalene dicarbaldehyde, diphenyl-dimethanal, Double (diformyl phenyl) methane, double (diformyl phenyl) propane, benzene trioxin etc., but it is not particularly limited in these.They It can be used alone, or combine two or more and use.Wherein, from assigning high-fire resistance aspect, benzene first is preferably used Aldehyde, hydroxy benzaldehyde, fluorobenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, tolyl aldehyde, dimethylbenzaldehyde, ethylamino benzonitrile Aldehyde, propylbenzaldehyde, butyl benzaldehyde, cyclohexyl benzene formaldehyde, biphenylcarboxaldehyde, naphthaldehyde, anthraldehyde, formaldehyde, pyrene formaldehyde, second two Aldehyde, glutaraldehyde, OPA, naphthalene dicarbaldehyde, diphenyl-dimethanal, anthracene dicarbaldehyde, double (diformyl phenyl) methane, double (two Fonnylphenyl) propane, benzene trioxin.

As foregoing ketone, for example, it can enumerate：Acetone, MEK, cyclobutanone, cyclopentanone, cyclohexanone, norborneol ketone, Three cyclohexanone, three ring decanones, Buddha's warrior attendant alkanone, Fluorenone, benzfluorenone, acenaphthenequinone, acenaphthene ketone, anthraquinone etc., but it is not particularly limited in these. They can be used alone or two or more is applied in combination.Wherein, from assigning high heat resistance aspect, preferably use Cyclopentanone, cyclohexanone, norborneol ketone, three cyclohexanone, three ring decanones, Buddha's warrior attendant alkanone, Fluorenone, benzfluorenone, acenaphthenequinone, acenaphthene ketone, anthracene Quinone.

On the acid catalyst used in above-mentioned reaction, it can suitably select to use from known acid catalyst, not have It is particularly limited to.As such acid catalyst, inorganic acid, organic acid are it is well known that as their concrete example, Ke Yiju Go out：The inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, oxalic acid, malonic acid, butanedioic acid, adipic acid, decanedioic acid, lemon Acid, fumaric acid, maleic acid, formic acid, p-methyl benzenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, fluoroform sulphur The lewis acids such as the organic acids such as acid, benzene sulfonic acid, naphthalene sulfonic acids, naphthalenedisulfonic acid, zinc chloride, aluminium chloride, iron chloride, boron trifluoride or Solid acids such as person's silico-tungstic acid, phosphotungstic acid, silicomolybdic acid or phosphomolybdic acid etc., but it is not particularly limited in these.Wherein, from the sight of manufacturing Point sets out, preferably organic acid and solid acid, from being readily available, is easily processed etc. from the viewpoint of manufacturing, preferably uses hydrochloric acid Or sulfuric acid.It should be noted that on acid catalyst, can be used alone or two or more is applied in combination.In addition, acid catalysis The consumption of agent can suitably be set according to species and then reaction condition of the raw material used and the catalyst used etc., not had It is particularly limited to, is 0.01~100 mass parts preferably with respect to the mass parts of reaction raw materials 100.

Reaction dissolvent can be used when carrying out above-mentioned reaction.As reaction dissolvent, as long as the aldehydes or ketone and phenol that use The reaction of class or thiophenols is just not particularly limited, and can suitably select to use from known solvent, for example can example Show：Water, methanol, ethanol, propyl alcohol, butanol, tetrahydrofuran, dioxanes, glycol dimethyl ether, ethylene glycol diethyl ether or they Mixed solvent etc..It should be noted that solvent can be used alone or two or more is applied in combination.In addition, these solvents Consumption can suitably be set according to species and then reaction condition of the raw material used and the acid catalyst used etc..As upper The consumption of solvent is stated, is not particularly limited, preferably with respect to the scope that the mass parts of reaction raw materials 100 are 0~2000 mass parts.Enter And, the reaction temperature of above-mentioned reaction can suitably be selected according to the reactivity of reaction raw materials.As above-mentioned reaction temperature, do not have It is particularly limited to, usually 10~200 DEG C of scope.As the compound shown in the formula (1) of present embodiment, in order to form oxygen Miscellaneous anthracene structure or thioxanthene structure, preferable reaction temperature are high, specifically preferably 60~200 DEG C of scope.It should be noted that anti- Induction method can suitably select known method and use, and be not particularly limited, there are as below methods：By phenols or thiophenols, aldehyde The method that class or ketone, acid catalyst are put into the lump；Phenols or thiophenols, aldehydes or ketone are added dropwise in presence of an acid catalyst Method.After polycondensation reaction terminates, the separation of gained compound can be carried out according to conventional method, be not particularly limited.For example, In order to which unreacting material, acid catalyst for will existing in system etc. are removed, 130~230 are risen to using the temperature of reactor is made DEG C, removed with 1~50mmHg or so and evaporate into the conventional method that grades, so as to obtain the compound as object.

As preferred reaction condition, relative to 1 mole of aldehydes or ketone, phenols or 1 mole of thiophenols~surplus are used 0.001~1 mole of amount and acid catalyst, at ambient pressure, with 50~150 DEG C, make it react 20 minutes~100 hours or so, from And carry out.

After reaction terminates, object can be separated by known method.For example, concentration of reaction solution, adding pure water makes instead Answer product to separate out, be cooled to after room temperature, carrying out filtering separates it, by filtering, after obtained solids is dried, pass through post Chromatography is isolated and purified with accessory substance, is carried out distillation and is removed solvent, filtering, dries, can obtain object i.e. as previously described formula (1) compound of the precursor of the compound shown in.

The precursor compound obtained by preceding method can be by known method, for example, by least one benzene phenolic hydroxyl group Hydrogen atom be substituted by univalent perssad of carbon number 1~30 etc., can obtain as the chemical combination shown in the previously described formula (1) of object Thing.

The method that the hydrogen atom of benzene phenolic hydroxyl group is substituted by the univalent perssad of carbon number 1~30 is not particularly limited, for example, Can be in the presence of base catalyst, using based on the de-hydrogen halide for making foregoing precursor compound be reacted with halogenated hydrocarbon compound And obtain.

As foregoing halogenated hydrocarbon compound, it is not particularly limited, is adapted to the halogenated hydrocarbon compound using carbon number 1~30.Halogen For hydrocarbon compound by by straight-chain alkyl, branched alkyl, alicyclic type hydrocarbon, aromatic hydrocarbyl and their group of more than two The group formed is closed to constitute with halogen atom.Herein, for foregoing alicyclic type hydrocarbon, also comprising bridging ring type alkyl.The halogenated hydrocarbons Compound can have double bond, hetero atom or other kinds of halogen atom.

Foregoing halogenated hydrocarbon compound can for example be enumerated：Chloromethanes, bromomethane, iodomethane, chloropropane, N-Propyl Bromide, iodine third Alkane, chlorobutane, NBB, iodobutane, chloroheptane, heptyl bromide, iodine heptane, chlorohexane, bromohexane, iodohexane, chlorodecane, the bromine last of the ten Heavenly stems Compound group shown in alkane, iodine decane or following formula (5) etc., but it is not particularly limited in these.They can be used alone, Or combine two or more and use.

In previously described formula (5), Y represents chlorine atom, bromine atoms or iodine atom.

In the organic solvents such as dimethylformamide, in base catalyst (sodium carbonate, potassium carbonate, triethylamine, ammonia or hydroxide Sodium etc.) in the presence of, relative to 1 mole of foregoing precursor compound, with 0~150 DEG C, make 0.1~10 mole of halogenated hydrocarbon compound Reaction 0.5~20 hour or so., can be by least one benzene phenolic hydroxyl group in foregoing gained precursor compound by the reaction It is converted into alkoxy.Then, filtered, using the cleaning of the alcohols such as methanol, washing, using the separation of filtering after, make its do It is dry, so as to obtain the compound shown in previously described formula (1).

The molecular weight of compound shown in previously described formula (1) is not particularly limited, and weight average molecular weight Mw is preferably 350~ 5000th, 400~3000 are more preferably.It should be noted that above-mentioned Mw can be by the method described in embodiment described later Determine.

[resin]

Compound shown in previously described formula (1) can directly be used as photoetching with substrate film formation material.Alternatively, it is also possible to Used as using compound resin as obtained from monomer shown in previously described formula (1).For example, it is also possible to as making previously described formula (1) compound shown in and resin obtained from the compound reaction with crosslinking reactivity and use.As with previously described formula (1) Shown compound is resin obtained from monomer, for example, can enumerate：Resin with the structure shown in following formula (2). That is, the photoetching substrate film formation material of present embodiment can contain the resin with the structure shown in following formula (2).

(in formula (2), X separately represents oxygen atom or sulphur atom or for without crosslinking, R¹For singly-bound or carbon number 1~ 30 2n valency groups, the alkyl optionally has the aryl of alicyclic type hydrocarbon, double bond, hetero atom or carbon number 6~30, R²Independently Ground is the straight-chain of carbon number 1~10, the alkyl of branched or ring-type, the aryl of carbon number 6~10, the alkenyl of carbon number 2~10, carbon The alkoxy of number 1~30, the aryloxy group or hydroxyl of carbon number 6~30, herein, R²In at least one be carbon number 1~30 alkoxy Or the aryloxy group of carbon number 6~30, R³It is separately the straight-chain or the alkylidene of branched of singly-bound or carbon number 1~20, m² Separately be 1~5 integer, the integer that p is separately 0 or 1, n are 1~4.)

In previously described formula (2), X separately represents oxygen atom or sulphur atom or for without crosslinking.Herein, X is without crosslinking Situation refer to, the structure shown in formula (2) be following formula (2B) shown in structure.

(in formula (2B), R¹、R²、R³、m², n and p with it is foregoing same.)

In previously described formula (2), R¹For singly-bound or the 2n valency groups of carbon number 1~30, by the R¹Connect each aromatic rings.Herein, 2n Valency group can have the aryl of alicyclic type hydrocarbon, double bond, hetero atom or carbon number 6~30.

R²It is separately the alkyl selected from straight-chain, branched or ring-type by carbon number 1~10, carbon number 6~10 Aryl, the alkenyl of carbon number 2~10, the alkoxy of carbon number 1~30, the aryloxy group of carbon number 6~30 and hydroxyl composition group in 1 Valency group, m is respectively connected with aromatic rings²It is individual.Herein, R²In at least one be carbon number 1~30 alkoxy or carbon number 6~30 Aryloxy group.

R³It is separately the straight-chain or the alkylidene of branched of singly-bound or carbon number 1~20.

m²Separately be 1~5 integer, the integer that p is separately 0 or 1, n are 1~4.Need explanation It is that foregoing 2n valencys group refers to, is identical meanings with the content described in the explanation of previously described formula (1).

Herein, from the viewpoint of the heat resistance formed based on upright and outspoken structure is improved, the structure shown in previously described formula (2) is preferred For the structure shown in following formula (2A).

(in formula (2A), R¹、R²、R³、m², n and p with it is foregoing same.)

Herein, from importing R⁵O groups and the degree of cross linking during baking produced improves the aspect that caused heat resistance is improved Set out, the structure shown in previously described formula (2A) is preferably the structure shown in following formula (2A-1).

(in formula (2A-1), R¹、R⁴、R⁵、m³、m⁴, n and p with it is foregoing same.)

In addition, from the viewpoint of safety solvent dissolubility is improved, the structure shown in previously described formula (2B) is preferably following formula Structure shown in (2B-1).

(in formula (2B-1), R¹、R⁴、R⁵、m³、m⁴, n and p with it is foregoing same.)

As the compound with crosslinking reactivity, as long as the compound oligomer represented by previously described formula (1) can be made The compound of change, is just not particularly limited, and can use known compound.As its concrete example, for example, it can enumerate：Aldehyde, Ketone, carboxylic acid, acid halide, halogen contained compound, amino-compound, imino-compound, isocyanates, the change containing unsaturated alkyl Compound etc., but it is not particularly limited in these.

As the concrete example of the resin with the structure shown in previously described formula (2), be not limited to it is following, can enumerate by with Condensation reaction as the aldehyde of the compound with crosslinking reactivity etc. is by the compound novolaks shown in previously described formula (1) Obtained resin.

Herein, as the aldehyde used when carrying out novolaks to the compound shown in previously described formula (1), for example, it can lift Go out：Formaldehyde, metaformaldehyde, paraformaldehyde, benzaldehyde, acetaldehyde, propionic aldehyde, phenylacetaldehyde, benzenpropanal, hydroxy benzaldehyde, chlorobenzaldehyde, Nitrobenzaldehyde, tolyl aldehyde, ethylo benzene formaldehyde, butyl benzaldehyde, biphenylcarboxaldehyde, naphthaldehyde, anthraldehyde, formaldehyde, pyrene first Aldehyde, furfural etc., but it is not particularly limited in these.Wherein preferred formaldehyde.It should be noted that these aldehydes can be used alone 1 Plant or two or more is applied in combination.In addition, the consumption of above-mentioned aldehydes is not particularly limited, relative to the change shown in previously described formula (1) 1 mole of compound, preferably 0.2~5 mole, more preferably 0.5~2 mole.

Compound shown in previously described formula (1) and in the condensation reaction of aldehyde, can also use acid catalyst.On being used herein as Acid catalyst, can from known acid catalyst suitably selection use, be not particularly limited.It is used as such acid catalysis Agent, inorganic acid, organic acid are it is well known that as their concrete example, can enumerate：Hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, It is the inorganic acids such as hydrofluoric acid, oxalic acid, malonic acid, butanedioic acid, adipic acid, decanedioic acid, citric acid, fumaric acid, maleic acid, formic acid, right Toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzene sulfonic acid, naphthalene sulfonic acids, naphthalenedisulfonic acid Deng the lewis acids such as organic acid, zinc chloride, aluminium chloride, iron chloride, boron trifluoride or silico-tungstic acid, phosphotungstic acid, silicomolybdic acid or phosphorus Solid acids such as molybdic acid etc., but it is not particularly limited in these.Wherein, from the viewpoint of manufacturing, preferably organic acid and solid acid, From being readily available, it is easily processed etc. from the viewpoint of manufacturing, preferably hydrochloric acid or sulfuric acid.It should be noted that on acid catalysis Agent, can be used alone or two or more is applied in combination.In addition, the consumption of acid catalyst according to the raw material used and can make The species of acid catalyst and then suitably set, be not particularly limited according to reaction condition etc., it is former preferably with respect to reaction It is 0.01~100 mass parts to expect 100 mass parts.It should be noted that with indenes, hydroxyl indenes, benzofuran, hydroxyl anthracene, acenaphthylene, Biphenyl, bis-phenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4 vinyl cyclohexene, norbornadiene, 5- vinyl norbornenes- , can be without using aldehyde when 2- alkene, australene, nopinene, limonene etc. have the compound progress copolyreaction of unconjugated double bond Class.

Compound shown in previously described formula (1) and in the condensation reaction of aldehyde, can also use reaction dissolvent.As in the polycondensation Reaction dissolvent, can from known solvent suitably selection use, be not particularly limited, for example, can enumerate：Water, methanol, Ethanol, propyl alcohol, butanol, tetrahydrofuran, dioxanes or their mixed solvent etc..It should be noted that solvent can individually make With a kind or two or more is applied in combination.

In addition, the consumption of these solvents can according to the species of the raw material used and the acid catalyst used so that according to Reaction condition etc. is suitably set.As the consumption of above-mentioned solvent, it is not particularly limited, preferably with respect to the matter of reaction raw materials 100 Measure the scope that part is 0~2000 mass parts.

And then, reaction temperature can suitably be selected according to the reactivity of reaction raw materials, be not particularly limited.As above-mentioned The scope of reaction temperature, usually 10~200 DEG C.It should be noted that reaction method can suitably select known method and Use, be not particularly limited, there are as below methods：The side that compound shown in previously described formula (1), aldehydes, catalyst are put into the lump Method；Compound, the method for aldehydes shown in previously described formula (1) are added dropwise in the presence of a catalyst.After polycondensation reaction terminates, gained The separation of compound can be carried out conventionally, be not particularly limited.For example it is present in unreacted in system to remove Raw material, catalyst etc., can be by using making the temperature of reactor rise to 130~230 DEG C, 1~50mmHg's or so Under the conditions of remove and evaporate into and grade usual way to obtain the resin through novolaks as target product.

Herein, the resin with the structure shown in previously described formula (2) can be the homopolymerization of the compound shown in previously described formula (1) Thing, or the copolymer with other phenols.Herein as copolymerizable phenols, for example, it can enumerate：Phenol, cresols, two Methylphenol, pseudocuminol, butylphenol, phenylphenol, diphenyl phenol, naphthyl phenol, resorcinol, methylresorcinol two Phenol, catechol, butyl-catechol, metoxyphenol, metoxyphenol, propylphenol, pyrogallol, thymol etc., but It is not limited to these.

In addition, the resin with the structure shown in previously described formula (2) can also be with addition to above-mentioned other phenols can Copolymer obtained from the monomer copolymerization of polymerization.As the comonomer, for example, it can enumerate：Naphthols, methyl naphthols, methoxy Base naphthols, dihydroxy naphthlene, indenes, hydroxyl indenes, benzofuran, hydroxyl anthracene, acenaphthylene, biphenyl, bis-phenol, trisphenol, dicyclopentadiene, four Hydrogen indenes, 4 vinyl cyclohexene, norbornadiene, vinyl norbornene, firpene, limonene etc., but it is not particularly limited in this A bit.It should be noted that the resin with the structure shown in previously described formula (2) can for the compound shown in previously described formula (1) with it is upper State more than 2 yuan (such as 2~4 yuan are) copolymer of phenols, or compound and above-mentioned copolymerization shown in previously described formula (1) More than 2 yuan (such as 2~4 yuan are) copolymers of monomer, can also for the compound shown in previously described formula (1) and above-mentioned phenols with it is upper State more than 3 yuan (such as 3~4 yuan are) copolymer of comonomer.

It should be noted that the molecular weight of the resin with the structure shown in previously described formula (2) is not particularly limited, preferably gather The weight average molecular weight (Mw) of styrene conversion is 500~30000, is more preferably 750~20000.In addition, from improve cross-linking efficiency And suppress in bakeing from the viewpoint of volatile ingredient, the molecular weight of the resin with the structure shown in previously described formula (2) preferably divides Divergence (weight average molecular weight Mw/ number-average molecular weight Mn) is in the range of 1.2~7.

Become easier to from the viewpoint of waiting, compound shown in previously described formula (1) and/or have from the application of wet processing The resin of structure shown in formula (2) is preferably the high resin of the dissolubility to solvent.More specifically, preferred pair 1- methoxyl groups- The solubility of 2- propyl alcohol (PGME) or propylene glycol methyl ether acetate (PGMEA) is more than 10 mass %.Herein, to PGME or PGMEA solubility is defined as the " quality ÷ (matter of quality+solvent of compound and/or resin of compound and/or resin Amount) × 100 (quality %) ".For example, when aforesaid compound and/or resin 10g are evaluated as dissolving relative to PGMEA90g, representing Aforesaid compound and/or resin when being evaluated as insoluble, are represented the situation that PGMEA solubility is " more than 10 mass % " The solubility is the " situation less than 10 mass % ".

[photoetching substrate film formation material]

The photoetching substrate film formation material of present embodiment contains：Selected from by the compound of present embodiment and this reality At least one kind of material in the group for the resin composition for applying mode.More specifically, the photoetching of present embodiment basilar memebrane formation material Material contains：Selected from as the compound shown in previously described formula (1)；With, as the compound shown in previously described formula (1) with crosslinking reactivity Compound reaction obtained from resin constitute group at least one kind of material.

When the photoetching of present embodiment includes the organic solvent as any condition described later with substrate film formation material, this The compound of embodiment and/or the content of the resin of present embodiment are not particularly limited, relative to including organic solvent The mass parts of total amount 100, preferably 1~33 mass parts, more preferably 2~25 mass parts, more preferably 3~20 mass parts.

The photoetching substrate film formation material of present embodiment as needed can also be comprising crosslinking agent, acid agent, organic The other compositions such as solvent.Hereinafter, these any conditions are illustrated.

[crosslinking agent]

From the viewpoint of mutually mixed (intermixing) etc. is suppressed, the photoetching substrate film formation material of present embodiment Crosslinking agent can also be contained as needed.As the concrete example of workable crosslinking agent in present embodiment, it can enumerate：Trimerization Cyanamide compound, guanamines compound, glycoluril compounds or carbamide compound, epoxide, thio epoxide, isocyanates Compound, azido compound, containing double bonds such as alkene ethers and it is selected from methylol, alkoxy methyl, pivaloyloxymethyl Compound that at least one group is replaced etc., but it is not particularly limited in these.It should be noted that these crosslinking agents can be single Solely use a kind or two or more is applied in combination.In addition, they can be used as additive, can by these crosslinkable groups with The form of side base imported into polymer lateral chain.Alternatively, it is also possible to use the compound for containing hydroxyl as crosslinking agent.

As the concrete example of melamine compound, it is not limited to following, can enumerates：Hexamethylolmelamine, six Methoxy melamine, 1~6 methylol of hexamethylolmelamine are through compound obtained from methoxymethylated Or its mixture, hexa methoxy ethyl melamine, six pivaloyloxymethyl melamines, 1~6 of hexamethylolmelamine Methylol is through compound obtained from pivaloyloxymethyl or its mixture etc..As the concrete example of epoxide, do not limit In following, it can enumerate：Three (2,3- glycidyl) isocyanuric acid esters, Pehanorm triglycidyl ether, trihydroxy methyl Propane triglycidyl ether, trihydroxyethyl ethane triglycidyl ether etc..

As the concrete example of guanamines compound, it is not limited to following, can enumerates：Tetra methylol guanamines, tetramethoxy first Base guanamines, 1~4 methylol of tetra methylol guanamines are through compound or its mixture, tetramethyl obtained from methoxymethylated Epoxide ethyl guanamines, four acyloxy guanamines, 1~4 methylol of tetra methylol guanamines obtained from pivaloyloxymethyl through changing Compound or its mixture etc..As the concrete example of glycoluril compounds, it is not limited to following, can enumerates：Tetramethylol glycoluril, four Methoxyl group glycoluril, tetramethoxymethylglycoluril, 1~4 methylol of tetramethylol glycoluril are through obtained from methoxymethylated Compound or its mixture, tetramethylol glycoluril 1~4 methylol is through compound obtained from pivaloyloxymethyl or it is mixed Compound etc..As the concrete example of carbamide compound, it is not limited to following, can enumerates：Tatramethylol urea, tetramethoxymethyl urea, 1~4 methylol of tatramethylol urea is through compound or its mixture, tetramethoxy ethyl carbamide obtained from methoxymethylated Deng.

As the concrete example of the compound containing alkene ether, it is not limited to following, can enumerates：Ethylene glycol divinyl Ether, triethylene glycol divinyl ether, 1,2- propane diols divinyl ether, 1,4- butanediols divinyl ether, tetramethylene glycol divinyl Ether, neopentyl glycol divinyl ether, trimethylolpropane tris vinethene, hexylene glycol divinyl ether, 1,4- cyclohexanediol divinyls ether, Pentaerythrite triethylene ether, the vinethene of pentaerythrite four, the vinethene of D-sorbite four, the vinethene of D-sorbite five, trihydroxy methyl Propane triethylene ether etc..

The photoetching of present embodiment is with substrate film formation material, and the content of crosslinking agent is not particularly limited, relative to this The compound of embodiment and/or the mass parts of the content of the resin of present embodiment 100, preferably 5~50 mass parts, more preferably For 10~40 mass parts.By being set to above-mentioned preferred scope, so that there have suppression to mix (mixing) with resist layer to be existing The tendency of elephant, is also improved anti-reflection effect, improves the tendency of the film formative after crosslinking.

[acid agent]

Promote from further from the viewpoint of cross-linking reaction based on heat etc., the photoetching basilar memebrane shape of present embodiment It can contain acid agent as needed into material.As acid agent, have as is generally known in the art produced by thermally decomposing acid material, Material of acid etc. is produced by light irradiation, can be used.

As acid agent, it can enumerate：

1) salt of following formulas (P1a-1), (P1a-2), (P1a-3) or (P1b),

2) diazomethane derivative of following formulas (P2),

3) the glyoxime derivative of following formulas (P3),

4) the bis sulfone derivative of following formulas (P4),

5) sulphonic acid ester of the N- hydroxyimide compounds of following formulas (P5),

6) β -one sulfonic acid,

7) two sulfone derivatives,

8) nitrobenzyl sulfonate derivatives,

9) sulfonate derivatives

Deng, but it is not particularly limited in these.Make it should be noted that these acid agents can be used alone or combine Use two or more.

In above-mentioned formula, R^101a、R^101b、R^101cStraight-chain, branched or the ring-type of carbon number 1~12 are represented independently of one another Alkyl, alkenyl, oxoalkyl group or oxo alkenyl, the aralkyl or aryl oxide of the aryl of carbon number 6~20 or carbon number 7~12 Substituted alkyl, part or all of the hydrogen atom of these groups can be replaced by alkoxy etc..In addition, R^101bAnd R^101cCan be with shape Cyclization, in the case where forming ring, R^101b、R^101cThe alkylidene of carbon number 1~6 is represented independently of one another.K^-Represent that non-nucleophilic is anti- Ion.R^101d、R^101e、R^101f、R^101gRepresent independently of one another in R^101a、R^101b、R^101cOn the basis of add hydrogen atom.R^101dWith R^101e、R^101dAnd R^101eAnd R^101fRing can be formed, in the case where forming ring, R^101dAnd R^101eAnd R^101dAnd R^101eAnd R^101f There is the heteroaromatic ring of the nitrogen-atoms in formula in the alkylidene or expression ring that represent carbon number 3~10.

Above-mentioned R^101a、R^101b、R^101c、R^101d、R^101e、R^101f、R^101gIt can be same to each other or different to each other.Specifically, make For alkyl, it is not limited to following, for example, can enumerates：Methyl, ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, Amyl group, hexyl, heptyl, octyl group, cyclopenta, cyclohexyl, suberyl, Cvclopropvlmethvl, 4- methylcyclohexyls, cyclohexyl methyl, Norborny, adamantyl etc..As alkenyl, it is not limited to following, for example, can includes：Vinyl, pi-allyl, acrylic, Cyclobutenyl, hexenyl, cyclohexenyl group etc..As oxoalkyl group, it is not limited to following, for example, can enumerates：2- oxocyclopentyls, 2- oxocyclohexyls etc. and 2- oxopropyls, 2- cyclopenta -2- oxoethyls, 2- cyclohexyl -2- oxoethyls, 2- (4- first Butylcyclohexyl) -2- oxoethyls etc..As oxo alkenyl, it is not limited to following, for example, can enumerates：2- oxo -4- cyclohexene Base, 2- oxo -4- acrylic etc..As aryl, it is not limited to following, for example, can enumerates：Phenyl, naphthyl etc., to methoxyl group Phenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyl phenenyl, to alcoxyls such as tert .- butoxyphenyl, a tert .- butoxyphenyls Base phenyl；2- aminomethyl phenyls, 3- aminomethyl phenyls, 4- aminomethyl phenyls, ethylphenyl, 4- tert-butyl-phenyls, 4- butyl phenyls, diformazan The alkyl phenyls such as base phenyl；The alkyl naphthyls such as methyl naphthyl, ethyl naphthyl；The alkoxynaphtalenes such as methoxyl group naphthyl, ethoxynaphthyl Base；The dialkyl group naphthyls such as dimethyl naphthyl, diethyl naphthyl；The dialkoxy naphthyls such as dimethoxy naphthyl, diethoxy naphthyl Deng.As aralkyl, it is not limited to following, for example, can enumerates：Benzyl, phenylethyl, phenethyl etc..It is used as aryl oxolanyl alkane Base, is not limited to following, for example, can enumerate：2- phenyl -2- oxoethyls, 2- (1- naphthyls) -2- oxoethyls, 2- (2- naphthalenes Base) the 2- aryl -2- oxoethyls such as -2- oxoethyls etc..It is used as K^-Non-nucleophilic counter ion, be not limited to it is following, for example It can enumerate：The halide ions such as chloride ion, bromide ion；Fluoroform sulphonate, 1,1,1- HFC-143as sulfonate, The fluoroalkyl sulfonates such as nine fluorine butane sulfonate；Toluene fulfonate, benzene sulfonate, 4- fluorobenzene sulfonate, the fluorine of 1,2,3,4,5- five The arylsulphonates such as benzene sulfonate；Alkylsulfonates such as mesylate, butane sulfonate etc..

In addition, R^101d、R^101e、R^101f、R^101gIn the case that there is the heteroaromatic ring of the nitrogen-atoms in formula in ring, As the heteroaromatic ring, it is not limited to following, imdazole derivatives (such as imidazoles, 4-methylimidazole, 4- first can be exemplified Base -2- phenylimidazoles etc.), pyrazole derivatives, Furazan Derivatives, pyrroline derivative (such as pyrrolin, 2- methyl isophthalic acid-pyrroles Quinoline etc.), pyrrolidin derivatives (such as pyrrolidines, N- crassitudes, pyrrolidones, 1-METHYLPYRROLIDONE), imidazoline Derivative, imidazolidine derivative, pyridine derivate (for example pyridine, picoline, ethylpyridine, propyIpyridine, butyl-pyridinium, 4- (1- butyl amyl group) pyridine, lutidines, trimethylpyridine, triethyl group pyridine, phenylpyridine, 3- methyl -2- phenyl pyrazolines Pyridine, 4- tert .-butylpyridines, hexichol yl pyridines, benzyl pyridine, methoxypyridine, butoxy pyridine, dimethoxy-pyridine, 1- first Base -2- pyridones, 4- pyrollidinopyridines, 1-methyl-4-phenylpyridinium, 2- (1- ethyl propyls) pyridine, aminopyridine, diformazan Base aminopyridine etc.), pyridyl derivatives, pyrimidine derivatives, pyrazines derivatives, pyrazoline derivative, pyrazolidine derivatives, piperidines Derivative, bridged piperazine derivatives, morpholine derivative, indole derivatives, isoindole derivatives, 1H- indazole derivatives, indoline derivative Thing, quinoline (such as quinoline, 3- quinolinecarbonitriles), isoquinilone derivatives, cinnoline derivatives, quinazoline derivant, quinoline Quinoline derivant, phthalazine derivatives, purine derivative, piperidine derivatives of talking endlessly, carbazole derivates, phenanthridine derivatives, acridine derivatives, phenol Oxazine derivatives, 1,10- phenanthroline derivatives, adenine derivative, adenosine derivative, guanine derivatives, guanosine derivative, urine Pyrimidine derivatives, uridine derivatives etc..

The salt of previously described formula (P1a-1) and formula (P1a-2) has the function as photoacid generator and thermal acid generator.Previously described formula (P1a-3) salt has the function as thermal acid generator.

In previously described formula (P1b), R^102a、R^102bThe alkane of the straight-chain, branched or ring-type of carbon number 1~8 is represented independently of one another Base.R¹⁰³Represent the alkylidene of the straight-chain, branched or ring-type of carbon number 1~10.R^104a、R^104bCarbon number 3 is represented independently of one another ~7 2- oxoalkyl groups.K^-Represent non-nucleophilic counter ion.

It is used as above-mentioned R^102a、R^102bConcrete example, be not limited to following, can enumerate：Methyl, ethyl, propyl group, isopropyl, Normal-butyl, sec-butyl, the tert-butyl group, amyl group, hexyl, heptyl, octyl group, cyclopenta, cyclohexyl, Cvclopropvlmethvl, 4- methyl cyclohexanes Base, cyclohexyl methyl etc..It is used as R¹⁰³Concrete example, be not limited to following, can enumerate：Methylene, ethylidene, propylidene, Asia The sub- ring penta of butyl, pentylidene, hexylidene, heptamethylene, octamethylene, nonylene, 1,4- cyclohexylidenes, 1,2- cyclohexylidenes, 1,3- Base, 1,4- cyclooctylenes, 1,4- cyclohexanedimethyleterephthalates etc..It is used as R^104a、R^104bConcrete example, be not limited to following, Ke Yiju Go out：2- oxopropyls, 2- oxocyclopentyls, 2- oxocyclohexyls, 2- oxo suberyl etc..K^-Can include with formula (P1a-1), (P1a-2) the implication identical material and in (P1a-3) illustrated.

In previously described formula (P2), R¹⁰⁵、R¹⁰⁶The straight-chain, branched or ring-type of carbon number 1~12 are represented independently of one another The aralkyl of alkyl or haloalkyl, the aryl of carbon number 6~20 or halogenated aryl or carbon number 7~12.

It is used as R¹⁰⁵、R¹⁰⁶Alkyl, be not limited to following, for example, can enumerate：Methyl, ethyl, propyl group, isopropyl, just Butyl, sec-butyl, the tert-butyl group, amyl group, hexyl, heptyl, octyl group, amyl group (amyl), cyclopenta, cyclohexyl, suberyl, norborneol Base, adamantyl etc..As haloalkyl, it is not limited to following, for example, can enumerates：Trifluoromethyl, 1,1,1- trifluoroethyls, 1,1,1- trichloroethyls, nine fluorine butyl etc..As aryl, it is not limited to following, for example, can enumerates：Phenyl, to methoxybenzene Base, m-methoxyphenyl, o-methoxyphenyl, ethoxyl phenenyl, to alkoxies such as tert .- butoxyphenyl, a tert .- butoxyphenyls Phenyl；2- aminomethyl phenyls, 3- aminomethyl phenyls, 4- aminomethyl phenyls, ethylphenyl, 4- tert-butyl-phenyls, 4- butyl phenyls, dimethyl The alkyl phenyls such as phenyl.As halogenated aryl, it is not limited to following, for example, can enumerates：Fluorophenyl, chlorphenyl, 1,2,3,4, 5- pentafluorophenyl groups etc..As aralkyl, it is not limited to following, for example, can enumerates：Benzyl, phenethyl etc..

In previously described formula (P3), R¹⁰⁷、R¹⁰⁸、R¹⁰⁹Straight-chain, branched or the ring of carbon number 1~12 are represented independently of one another The alkyl or haloalkyl of shape；The aryl or halogenated aryl of carbon number 6~20；Or the aralkyl of carbon number 7~12.R¹⁰⁸、R¹⁰⁹Can Cyclic structure is formed to bond together, in the case where forming cyclic structure, R¹⁰⁸、R¹⁰⁹Each represent the straight chain of carbon number 1~6 The alkylidene of shape or branched.

It is used as R¹⁰⁷、R¹⁰⁸、R¹⁰⁹Alkyl, haloalkyl, aryl, halogenated aryl, aralkyl, can enumerate and R¹⁰⁵、R¹⁰⁶ The implication identical group of middle explanation.It should be noted that being used as R¹⁰⁸、R¹⁰⁹Alkylidene, be not limited to it is following, for example can be with Enumerate：Methylene, ethylidene, propylidene, butylidene, hexylidene etc..

(in formula (P4), R^101a、R^101bIt is same as described above.)

In previously described formula (P5), R¹¹⁰Represent the Asia of the arlydene, the alkylidene of carbon number 1~6 or carbon number 2~6 of carbon number 6~10 Alkenyl, the hydrogen atom of these groups part or all can with and then by carbon number 1~4 straight-chain or the alkyl of branched Or alkoxy, nitro, acetyl group or phenyl substitution.R¹¹¹Straight-chain, branched or the substituted alkyl of expression carbon number 1~8, Alkenyl or alkoxyalkyl, phenyl or naphthyl, part or all of the hydrogen atom of these groups can be with and then by following group Substitution：The alkyl or alkoxy of carbon number 1~4；The benzene that can be replaced by the alkyl of carbon number 1~4, alkoxy, nitro or acetyl group Base；The heteroaromatic group of carbon number 3~5；Or chlorine atom, fluorine atom.

Herein, as R¹¹⁰Arlydene, be not limited to following, for example, can enumerate：1,2- phenylenes, 1,8- naphthylenes Deng.As alkylidene, it is not limited to following, for example, can enumerates：Methylene, ethylidene, trimethylene, tetramethylene, phenyl Ethylidene, norbornane -2,3- diyls etc..As alkenylene, it is not limited to following, for example, can enumerates：1,2- ethenylidenes, 1- phenyl -1,2- ethenylidenes, 5- ENB -2,3- diyls etc..It is used as R¹¹¹Alkyl, can enumerate and R^101a~R^101cPhase Same group.As alkenyl, it is not limited to following, for example, can enumerates：Vinyl, 1- acrylic, pi-allyl, 1- cyclobutenyls, 3- cyclobutenyls, prenyl, 1- pentenyls, 3- pentenyls, 4- pentenyls, dimethyl-allyl, 1- hexenyls, 3- hexenes Base, 5- hexenyls, 1- heptenyls, 3- heptenyls, 6- heptenyls, 7- octenyls etc..As alkoxyalkyl, be not limited to Under, it can such as enumerate：Methoxy, ethoxyl methyl, propoxy methyl, butoxymethyl, amoxy methyl, hexyloxy Methyl, epoxide methyl in heptan, methoxy ethyl, ethoxyethyl group, Among, butoxyethyl group, amoxy ethyl, hexyloxy Ethyl, methoxy-propyl, ethoxycarbonyl propyl, propoxypropyl, butoxypropyl, methoxybutyl, ethoxybutyl, propoxyl group Butyl, methoxypentyl, ethoxypentyl, methoxyethyl, Methoxyheptyl etc..

It should be noted that as so the alkyl of carbon number 1~4 that can be substituted, be not limited to it is following, for example can be with Enumerate：Methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, tert-butyl group etc..As the alkoxy of carbon number 1~4, do not limit In following, for example, it can enumerate：Methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, isobutoxy, tert-butoxy Deng.As the phenyl that can be replaced by the alkyl of carbon number 1~4, alkoxy, nitro or acetyl group, it is not limited to following, for example may be used To enumerate：Phenyl, tolyl, to tert .- butoxyphenyl, to acetylphenyl, p-nitrophenyl etc..It is used as the miscellaneous of carbon number 3~5 Aromatic group, is not limited to following, for example, can enumerate：Pyridine radicals, furyl etc..

As the concrete example of acid agent, it is not limited to following, can enumerates：Trifluoromethanesulfonic acid tetramethyl-ammonium, nine fluorine butane Sulfonic acid tetramethyl-ammonium, nine fluorine butane sulfonic acid triethyl ammoniums, nine fluorine butane sulfonic acid pyridines, camphorsulfonic acid triethyl ammonium, camphor sulphur Sour pyridine, nine fluorine butane sulfonic acid tetra-n-butyl ammoniums, nine fluorine butane sulfonic acid tetraphenyl ammoniums, p-methyl benzenesulfonic acid tetramethyl-ammonium, trifluoro Methanesulfonic acid diphenyl iodine, trifluoromethanesulfonic acid (to tert .- butoxyphenyl) phenyl-iodide, p-methyl benzenesulfonic acid diphenyl iodine, to first Benzene sulfonic acid (to tert .- butoxyphenyl) phenyl-iodide, trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (to tert .- butoxyphenyl) It is double (to tert .- butoxyphenyl) the phenyl sulfoniums of diphenyl sulfonium, trifluoromethanesulfonic acid, trifluoromethanesulfonic acid three (to tert .- butoxyphenyl) sulfonium, right Toluenesulfonic acid triphenylsulfonium, p-methyl benzenesulfonic acid (to tert .- butoxyphenyl) diphenyl sulfonium, p-methyl benzenesulfonic acid are double (to tert-butoxy benzene Base) phenyl sulfonium, p-methyl benzenesulfonic acid three (to tert .- butoxyphenyl) sulfonium, nine fluorine butane sulfonic acid triphenylsulfoniums, butane sulfonic acid triphenyl Sulfonium, trifluoromethanesulfonic acid trimethylsulfonium, p-methyl benzenesulfonic acid trimethylsulfonium, trifluoromethanesulfonic acid cyclohexyl methyl (2- oxocyclohexyls) Sulfonium, p-methyl benzenesulfonic acid cyclohexyl methyl (2- oxocyclohexyls) sulfonium, trifluoromethanesulfonic acid 3,5-dimethylphenyl sulfonium, p-methyl benzenesulfonic acid diformazan Base phenyl sulfonium, trifluoromethanesulfonic acid dicyclohexylphenylbismuthine sulfonium, p-methyl benzenesulfonic acid dicyclohexylphenylbismuthine sulfonium, the naphthyl of trifluoromethanesulfonic acid three Sulfonium, trifluoromethanesulfonic acid cyclohexyl methyl (2- oxocyclohexyls) sulfonium, trifluoromethanesulfonic acid (2- norbornenes) methyl (2- oxo rings Hexyl) sulfonium, ethylenebis [methyl (2- oxocyclopentyls) sulfonium trifluoro-methanyl sulfonate], 1,2 '-naphthyl carbonyl methyl tetrahydrochysene thiophene The salt such as fen fluoroform sulphonate；Double (benzenesulfonyl) diazomethanes, double (p-toluenesulfonyl) diazomethanes, double (diformazans Benzenesulfonyl) diazomethane, double (cyclohexylsulfonyl) diazomethanes, double (Cyclopentylsulfonyl) diazomethanes, double (normal-butyls Sulfonyl) diazomethane, double (iso-butylsulfonyl) diazomethanes, double (sec-butylsulfonyl) diazomethanes, double (n-propyl sulphurs Acyl group) diazomethane, double (isopropelsulfonyl) diazomethanes, double (tert. butylsulfonyl) diazomethanes, double (n-pentyl sulphonyl Base) diazomethane, double (isopentyl sulfonyl) diazomethanes, double (sec-amyl sulfonyl) diazomethanes, double (tertiary pentyl sulphonyl Base) diazomethane, 1- cyclohexylsulfonyls -1- (tert. butylsulfonyl) diazomethane, 1- cyclohexylsulfonyl -1- (tertiary pentyls Sulfonyl) diazomethane derivative such as diazomethane, 1- tertiary pentyl sulfonyls -1- (tert. butylsulfonyl) diazomethane；It is double (right Tosyl)-alpha-alpha-dimethyl glyoxime, double (p-toluenesulfonyl)-α-diphenyl glyoximes, double (p-toluenesulfonyls)- α-dicyclohexyl glyoxime, double (p-toluenesulfonyl) -2,3- pentanediones glyoximes, double (p-toluenesulfonyl) -2- methyl -3, 4- pentanediones glyoxime, double (normal butane sulfonyl)-alpha-alpha-dimethyl glyoximes, double (normal butane sulfonyl)-α-diphenyl second two Oxime, double (normal butane sulfonyl)-α-dicyclohexyl glyoximes, double (normal butane sulfonyl) -2,3- pentanediones glyoximes, it is double (just Butane sulfonyl) -2- methyl -3,4- pentanediones glyoxime, double (methane sulfonyl)-alpha-alpha-dimethyl glyoximes, double (fluoroforms Sulfonyl)-alpha-alpha-dimethyl glyoxime, double (1,1,1- HFC-143as sulfonyl)-alpha-alpha-dimethyl glyoximes, double (tertiary butane sulphonyl Base)-alpha-alpha-dimethyl glyoxime, double (PFO sulfonyl)-alpha-alpha-dimethyl glyoximes, double (Cyclohexanesulfonyl)-alpha, alpha-dimethyls It is base glyoxime, double (benzenesulfonyl)-alpha-alpha-dimethyl glyoximes, double (to fluorophenylsulphonyl)-alpha-alpha-dimethyl glyoximes, double (to uncle Butyl benzenesulfonyl)-alpha-alpha-dimethyl glyoxime, double (ditosyl)-alpha-alpha-dimethyl glyoximes, double (camphor sulfonyls)- The glyoxime derivative such as alpha-alpha-dimethyl glyoxime；Double Naphthylsulfonyl methane, double (trifluoromethyl sulfonyl) methane, double methyl sulphurs Sulfonyl methane, double ethylsulfonyl methane, double sulfonyl propyl methylmethanes, double isopropelsulfonyl methane, double (tolysulfonyl Base) the bis sulfone derivative such as methane, double benzenesulfonyl methane；2- cyclohexyl-carbonyls -2- (p-toluenesulfonyl) propane, 2- isopropyls The β -one sulfone derivatives such as carbonyl -2- (p-toluenesulfonyl) propane；The sulfone derivative of diphenyl two, the sulfone derivative of dicyclohexyl two etc. The nitrobenzyl sulfonic acid such as two sulfone derivatives, p-methyl benzenesulfonic acid -2,6- dinitros benzyl ester, p-methyl benzenesulfonic acid -2,4- dinitro benzyl esters Ester derivant；1,2,3- tri- (methanesulfonyloxy group) benzene, 1,2,3- tri- (trifluorometanesulfonyloxy) benzene, 1,2,3- tri- are (to first Phenylsulfonyloxy) sulfonate derivatives such as benzene；N-hydroxysuccinimide methanesulfonates, n-hydroxysuccinimide fluoroform sulphur Acid esters, n-hydroxysuccinimide ethane sulfonic acid ester, n-hydroxysuccinimide 1- propane sulfonic acids ester, n-hydroxysuccinimide 2- propane sulfonic acids ester, n-hydroxysuccinimide -1- pentanesulfonic acids ester, n-hydroxysuccinimide -1- perfluoroetane sulfonic acids ester, N- hydroxyls Base succinimide p-methyl benzenesulfonic acid ester, n-hydroxysuccinimide are to methoxy benzenesulfonic acid ester, n-hydroxysuccinimide 2- Chloroethanes sulphonic acid ester, n-hydroxysuccinimide benzene sulfonate, n-hydroxysuccinimide -2,4,6- tri-methyl p-toluenesulfonates ester, N-hydroxysuccinimide -1-naphthalene sulfonic aicd ester, n-hydroxysuccinimide 2- napsylates, N- hydroxyl -2- phenyl succinyl are sub- Amine methanesulfonates, N- hydroxy maleimides methanesulfonates, N- hydroxy maleimide ethane sulfonic acids ester, N- hydroxyl -2- phenyl Maleimide methanesulfonates, N- glutarimides methanesulfonates, N- glutarimides benzene sulfonate, N- hydroxyls are adjacent BIDA methanesulfonates, HP benzene sulfonate, HP fluoroform Sulphonic acid ester, HP p-methyl benzenesulfonic acid ester, N- hydroxyl naphthalimides methanesulfonates, N- hydroxyl naphthalenes two Carboximide benzene sulfonate, N- hydroxyl -5- ENB -2,3- dicarboximides methanesulfonates, N- hydroxyl -5- norborneols Alkene -2,3- dicarboximides triflate, N- hydroxyl -5- ENB -2,3- dicarboximide p-methyl benzenesulfonic acid Sulfonate derivatives of the N- hydroxyimide compounds such as ester etc..

Wherein, particularly preferably using trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (to tert .- butoxyphenyl) diphenyl Sulfonium, trifluoromethanesulfonic acid three (to tert .- butoxyphenyl) sulfonium, p-methyl benzenesulfonic acid triphenylsulfonium, p-methyl benzenesulfonic acid are (to tert-butoxy benzene Base) diphenyl sulfonium, p-methyl benzenesulfonic acid three (to tert .- butoxyphenyl) sulfonium, the naphthyl sulfonium of trifluoromethanesulfonic acid three, trifluoromethanesulfonic acid hexamethylene Ylmethyl (2- oxocyclohexyls) sulfonium, trifluoromethanesulfonic acid (2- norbornenes) methyl (2- oxocyclohexyls) sulfonium, 1,2 '-naphthyl The salt such as carbonvlmethyl thiophane fluoroform sulphonate；Double (benzenesulfonyl) diazomethanes, double (p-toluenesulfonyls) weight N-formyl sarcolysine alkane, double (cyclohexylsulfonyl) diazomethanes, double (normal-butyl sulfonyl) diazomethanes, double (iso-butylsulfonyl) diazonium Methane, double (sec-butylsulfonyl) diazomethanes, double (n-propyl sulfonyl) diazomethanes, double (isopropelsulfonyl) diazonium first The diazomethane derivatives such as alkane, double (tert. butylsulfonyl) diazomethanes；Double (p-toluenesulfonyl)-alpha-alpha-dimethyl glyoximes, The bis sulfone derivatives such as the glyoxime derivatives such as double (normal butane sulfonyl)-alpha-alpha-dimethyl glyoximes, double Naphthylsulfonyl methane；N- HOSu NHS methanesulfonates, n-hydroxysuccinimide triflate, n-hydroxysuccinimide -1- propane sulphurs Acid esters, n-hydroxysuccinimide -2- propane sulfonic acids ester, n-hydroxysuccinimide -1- pentanesulfonic acids ester, N- hydroxysuccinimidyl acyls The N- hydroxyls such as imines p-methyl benzenesulfonic acid ester, N- hydroxyl naphthalimides methanesulfonates, N- hydroxyl naphthalimide benzene sulfonates The sulfonate derivatives of base imide compound.

The photoetching of present embodiment is with substrate film formation material, and the content of acid agent is not particularly limited, relative to this The compound of embodiment and/or the mass parts of the content of the resin of present embodiment 100, it is preferably 0.1~50 mass parts, more excellent Elect 0.5~40 mass parts as.By being set to above-mentioned preferred scope, so that have the tendency of the sour quantitative change of production improves cross-linking reaction more, The tendency that (mixing) phenomenon is inhibited also is mixed with resist layer.

And then, from the viewpoint of bin stability etc. is improved, the photoetching substrate film formation material of present embodiment can To contain alkali compounds.

Alkali compounds, which is played, to be prevented by the work of quencher acid promotion cross-linking reaction, to acid of the micro generation of acid agent With.As such alkali compounds, for example, it can enumerate：Aliphatic primary, secondary or tertiary amine, mixing amine, aromatic amine Class, heterocyclic amine, the nitrogen-containing compound with carboxyl, the nitrogen-containing compound with sulfonyl, the nitrogen-containing compound with hydroxyl, Nitrogen-containing compound with hydroxy phenyl, alcohol nitrogen-containing compound, amide derivatives, imide derivative etc., but do not limit especially Due to these.

As the concrete example of Armeen class, it is not limited to following, can enumerates：It is ammonia, methylamine, ethamine, n-propylamine, different Propylamine, n-butylamine, isobutyl amine, sec-butylamine, tert-butylamine, amylamine, tertiary amylamine, cyclopentamine, hexylamine, cyclohexylamine, heptyl amice, octylame, nonyl Amine, decyl amine, lauryl amine, cetylamine, methylene diamine, ethylene diamine, tetren etc..It is used as aliphatic secondary amine Concrete example, is not limited to following, can enumerate：Dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, two isobutyls Amine, di-sec-butylamine, diamylamine, two cyclopentamines, dihexylamine, dicyclohexyl amine, two heptyl amices, dioctylamine, nonyl amine, didecylamine, two (ten Diamines), two (cetylamines), N, N- dimethylated methylene bases diamines, N, N- dimethylethylidenediamines, N, the ethylidene of N- dimethyl four Five amine etc..As the concrete example of aliphatic tertiary amine class, it is not limited to following, can enumerates：Trimethylamine, triethylamine, Tri-n-Propylamine, Tri-isopropyl amine, tri-n-butylamine, triisobutylamine, tri sec-butylamine, triamylamine, three cyclopentamines, trihexylamine, tricyclohexyltin amine, three heptyl amices, three Octylame, TNA trinonylamine, tridecylamine, three (lauryl amines), three (cetylamines), N, N, N ', N '-tetramethyl methylene diamine, N, N, N ', N '-tetramethylethylened, N, N, N ', N '-tetramethyl tetren etc..

In addition, as the concrete example of mixing amine, being not limited to following, it can enumerate：Dimethyl amine, Methylethyl third Amine, benzylamine, phenyl ethylamine, benzyl dimethylamine etc..As aromatic amine and the concrete example of heterocyclic amine, be not limited to it is following, can To enumerate：Anil (such as aniline, methylphenylamine, N-ethylaniline, N propyl aniline, N, accelerine, 2- Methylaniline, 3- methylanilines, 4- methylanilines, MEA, propyl group aniline, trimethylaniline, 2- nitroanilines, 3- nitros Aniline, 4- nitroanilines, 2,4- dinitroanilines, 2,6- dinitroanilines, 3,5- dinitroanilines, N, N- dimethyl toluidines Deng), (p-methylphenyl) diphenylamines, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, azole derivatives (for example The), such as pyrroles, 2H- pyrroles, 1- methylpyrroles, 2,4- dimethyl pyrroles, 2,5- dimethyl pyrroles, N- methylpyrroles oxazoles derive Thing (Li such as oxazole, isoxazoles etc.), thiazole (such as thiazole, isothiazole), imdazole derivatives (such as imidazoles, 4- first Base imidazoles, 4- methyl -2- phenylimidazoles etc.), pyrazole derivatives, Furazan Derivatives, pyrroline derivative (such as pyrrolin, 2- Methyl isophthalic acid-pyrrolin etc.), pyrrolidin derivatives (such as pyrrolidines, N- crassitudes, pyrrolidones, 1-METHYLPYRROLIDONE Deng), imidazolidine derivatives, imidazolidine derivative, pyridine derivate (for example pyridine, picoline, ethylpyridine, propyIpyridine, Butyl-pyridinium, 4- (1- butyl amyl group) pyridine, lutidines, trimethylpyridine, triethyl group pyridine, phenylpyridine, 3- methyl- 2- phenylpyridines, 4- tert .-butylpyridines, hexichol yl pyridines, benzyl pyridine, methoxypyridine, butoxy pyridine, dimethoxy pyrrole Pyridine, 1- methyl -2- pyridones, 4- pyrollidinopyridines, 1-methyl-4-phenylpyridinium, 2- (1- ethyl propyls) pyridine, amino pyrrole Pyridine, dimethyl aminopyridine etc.), pyridyl derivatives, pyrimidine derivatives, pyrazines derivatives, pyrazoline derivative, pyrazolidine derive Thing, piperidine derivative, bridged piperazine derivatives, morpholine derivative, indole derivatives, isoindole derivatives, 1H- indazole derivatives, Yin Diindyl quinoline derivant, quinoline (such as quinoline, 3- quinolinecarbonitriles), isoquinilone derivatives, cinnoline derivatives, quinazoline derivative Thing, quinoxaline derivant, phthalazine derivatives, purine derivative, piperidine derivatives of talking endlessly, carbazole derivates, phenanthridine derivatives, acridine spread out Biology, phenol oxazine derivatives, 1,10- phenanthroline derivatives, adenine derivative, adenosine derivative, guanine derivatives, guanosine spread out Biology, uracil derivative, uridine derivatives etc..

And then, as the concrete example of the nitrogen-containing compound with carboxyl, it is not limited to following, can enumerates：Aminobenzoic Acid, indole-carboxylic acid, amino acid derivativges (such as nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, group ammonia Acid, isoleucine, glycyl-leucine, leucine, methionine, phenylalanine, threonine, lysine, 3- Aminopyrazines- 2- carboxylic acids, methoxy propyl propylhomoserin) etc..As the concrete example of the nitrogen-containing compound with sulfonyl, following, Ke Yiju is not limited to Go out：3- pyridine-sulfonic acids, p-methyl benzenesulfonic acid pyridine etc..As the nitrogen-containing compound with hydroxyl, with the nitrogenous of hydroxy phenyl The concrete example of compound, alcohol nitrogen-containing compound, is not limited to following, can enumerate：2 hydroxy pyrimidine, amino cresols, 2,4- Quinoline diol, 3- indole-alcohols hydrate, MEA, diethanol amine, triethanolamine, N- ethyldiethanolamines, N, N- diethyls Ethylethanolamine, triisopropanolamine, 2,2 '-diethanolimine, 2- ethylaminoethanols, 3- amino -1- propyl alcohol, 4- amino-n-butyl alcohol, 4- (2- ethoxys) morpholine, 2- (2- ethoxys) pyridine, 1- (2- ethoxys) piperazine, 1- [2- (2- hydroxyl-oxethyls) ethyl] piperazine Piperazine, piperidine ethanol, 1- (2- ethoxys) pyrrolidines, 1- (2- ethoxys) -2-Pyrrolidone, 3- piperidyl -1,2- propane diols, 3- Pyrrolidinyl -1,2- propane diols, 8- hydroxyls julolidine, 3- quinuclidinols, 3- tropanols, 1- methyl -2- pyrrolidines ethanol, 1- nitrogen Third pyridine ethanol, N- (2- ethoxys) phthalimide, N- (2- ethoxys) Pyrazinamide etc..It is used as the tool of amide derivatives Style, is not limited to following, can enumerate：Formamide, N-METHYLFORMAMIDE, N,N-dimethylformamide, acetamide, N- methyl Acetamide, DMAC N,N' dimethyl acetamide, propionamide, benzamide etc..As the concrete example of imide derivative, be not limited to Under, it can enumerate：Phthalimide, succinimide, maleimide etc..

The photoetching of present embodiment is with substrate film formation material, and the content of alkali compounds is not particularly limited, relatively It is preferably 0.001~2 mass parts, more excellent in the compound and/or the mass parts of resin 100 of present embodiment of present embodiment Elect 0.01~1 mass parts as.By being set as above-mentioned preferred scope, so as to be improved bin stability and will not excessive damage The tendency of cross-linking reaction.

[organic solvent]

The photoetching substrate film formation material of present embodiment can also contain organic solvent.As organic solvent, as long as At least dissolve the compound of present embodiment and/or the resin of present embodiment, it is possible to appropriate to use known organic solvent.

As the concrete example of organic solvent, it can enumerate：The ketone such as acetone, MEK, methyl iso-butyl ketone (MIBK), cyclohexanone system is molten The cellosolve such as agent, propylene glycol monomethyl ether, propylene glycol methyl ether acetate series solvent, ethyl lactate, methyl acetate, ethyl acetate, The ester series solvents such as butyl acetate, isoamyl acetate, ethyl lactate, methoxy methyl propionate, hydroxy-methyl isobutyl acid, methanol, second Fragrant family hydrocarbon such as alcohol series solvent, toluene, dimethylbenzene, the methyl phenyl ethers anisoles such as alcohol, isopropanol, 1- ethyoxyl -2- propyl alcohol etc., but it is not special It is defined in these.These organic solvents can be used alone or combine two or more and use.

In above-mentioned organic solvent, from security aspect, particularly preferred cyclohexanone, propylene glycol monomethyl ether, propane diols Methyl ether acetate, ethyl lactate, hydroxy-methyl isobutyl acid, methyl phenyl ethers anisole.

The content of organic solvent is not particularly limited, from the viewpoint of dissolubility and film are upper, relative to this embodiment party The compound of formula and/or the mass parts of resin 100 of present embodiment, preferably 100~10000 mass parts, more preferably 200~ 5000 mass parts.

[other compositions]

In addition, for the purpose for assigning Thermocurable, controlling absorbance, the photoetching basilar memebrane formation material of present embodiment Material can contain other resins and/or compound.As such other resins and/or compound, it can enumerate：Naphthols tree The naphthol-modified resin of fat, xylene resin, the phenol-modified resin of naphthalene resin, polycarboxylated styrene, dcpd resin, (methyl) acrylate, dimethylacrylate, trimethyl acrylic ester, tetramethyl acrylate, vinyl naphthalene, polyace naphthylene etc. Resin containing cyclohexyl biphenyl, thiophene, the indenes such as resin, phenanthrenequione, fluorenes containing naphthalene nucleus etc. contain with heteroatomic heterocycle resin, Resin without aromatic ring；Rosin system resin, cyclodextrin, adamantane (many) alcohol, tristane (many) alcohol and their derivative The resin containing alicyclic structure such as thing or compound etc., but it is not particularly limited in these.And then, the photoetching base of present embodiment Bottom film formation material can also contain known additive, such as ultra-violet absorber, surfactant, colouring agent, nonionic It is surfactant.

[forming method of photoetching basilar memebrane and multilayer corrosion-resisting pattern]

The photoetching of present embodiment is formed with basilar memebrane by the photoetching of present embodiment with substrate film formation material.

In addition, the forming method of the corrosion-resisting pattern of present embodiment has following process：Process (A-1), uses this reality The photoetching for applying mode forms basilar memebrane with substrate film formation material on substrate；Process (A-2), formed on aforementioned substrates film to Few 1 layer photoresist layer；Process (A-3), after foregoing sequence (A-2), to the predetermined region of foregoing photoresist layer Illumination radiation line, is developed.

And then, the forming method of the circuit pattern of present embodiment has following process：Process (B-1), uses this reality The photoetching for applying mode forms basilar memebrane with substrate film formation material on substrate；Process (B-2), using containing the against corrosion of silicon atom Agent interlayer film material forms interlayer film on aforementioned substrates film；Process (B-3), in the preamble between form at least 1 on tunic The photoresist layer of layer；Process (B-4), after foregoing sequence (B-3), the predetermined region to foregoing photoresist layer is shone Penetrate radiation and developed, form corrosion-resisting pattern；Process (B-5), after foregoing sequence (B-4), by foregoing corrosion-resisting pattern Foregoing interlayer film is etched as mask, using obtained interlayer film pattern as etching mask to aforementioned substrates Film is etched, and obtained substrate film figure is etched as etching mask to substrate, and figure is thus formed on substrate Case.

As long as the photoetching of present embodiment is formed with basilar memebrane by foregoing photoetching with substrate film formation material, just it is formed Method is not particularly limited, can be using known method.For example, can be by being applied known to rotary coating, silk-screen printing etc. After foregoing photoetching is imparted on substrate by cloth method or print process etc. with substrate film formation material, makes organic solvent volatilization etc. and go Remove, be consequently formed basilar memebrane.In the formation of basilar memebrane, in order to suppress to mix (mixing) phenomenon with upper strata resist simultaneously And promote cross-linking reaction to carry out, preferably bakeed.In this case, stoving temperature is not particularly limited, preferably 80 In the range of~450 DEG C, it is more preferably 200~400 DEG C.In addition, the baking time is also not particularly limited, preferably 10~ In the range of 300 seconds.It should be noted that the thickness of basilar memebrane performance can be selected suitably according to demand, do not limit especially It is fixed, it is generally desirable to, preferably 30~20000nm or so, more preferably 50~15000nm.Make after basilar memebrane, preferably It is：In the case of 2 layer process, siliceous resist layer or the common individual layer resist formed by hydrocarbon, 3 layers of work are made thereon In the case of skill, siliceous intermediate layer is made thereon and then not siliceous individual layer resist layer is made thereon.In such case Under, as the photo anti-corrosion agent material for forming the resist layer, known material can be used.

Made on substrate after basilar memebrane, in the case of 2 layer process, siliceous resist layer can be made on the basilar memebrane Or the common individual layer resist formed by hydrocarbon, in the case of 3 layer process, siliceous centre can be made on the basilar memebrane Layer and then make not siliceous individual layer resist layer on the siliceous intermediate layer.In these cases, for forming resist layer Photo anti-corrosion agent material can from known material suitably selection use, be not particularly limited.

From resistance to oxygen etch aspect, the siliceous anticorrosive additive material of 2 layer process preferably uses poly- silsesquioxane Polymer based on the polymer of the silicon atoms such as alkane derivatives or vinyl silanes derivative, so containing organic solvent, The photo anti-corrosion agent material of acid agent, the as needed eurymeric containing alkali compounds etc..Herein as the polymerization of silicon atoms Thing, can use the known polymer used in this anticorrosive additive material.

As the siliceous intermediate layer of 3 layer process, the intermediate layer on polysilsesquioxane basis is preferably used.By making centre Layer has the effect as antireflection film, so as to have the tendency of effectively suppress reflection.For example, in 193nm exposure techniques In, contain a large amount of aromatic groups and the high material of substrate elching resistant is as basilar memebrane if using, there are k values to uprise, substrate The tendency uprised is reflected, but suppresses reflection by using intermediate layer, so as to make substrate be reflected into less than 0.5%.As Intermediate layer with this anti-reflection effect, exposes as 193nm and uses, preferably use and imported phenyl or with silicon-silicon bond Extinction group and the polysilsesquioxane that can be crosslinked by acid or heat.

Alternatively, it is also possible to use the intermediate layer by the formation of chemical gaseous phase deposition (CVD) method.Made as by CVD The high intermediate layer of the effect as antireflection film, be not limited to it is following, such as it is known to have SiON films.Generally compared with CVD, It is easier and there is the advantage in cost using the wet processings such as method of spin coating, silk-screen printing formation intermediate layer.Need explanation , the upper strata resist of 3 layer process is eurymeric or minus, can also be used and usually used individual layer resist phase Same material.

And then, the basilar memebrane of present embodiment can also as common individual layer resist antireflection film or be used for Suppress the base material of pattern collapse to use.Because the elching resistant that the basilar memebrane of present embodiment is used for substrate processing is excellent It is different, therefore can also expect the function as the hard mask processed for substrate.

In the case of using above-mentioned photo anti-corrosion agent material formation resist layer, the situation phase with forming above-mentioned basilar memebrane Together, the wet processings such as method of spin coating, silk-screen printing are preferably used.In addition, passing through the painting erosion resistant agent material such as method of spin coating Afterwards, prebake is generally carried out, the prebake is preferably carried out in 80~180 DEG C and 10~300 seconds of scope.Thereafter, according to routine Method is exposed, against corrosion so as to obtain by toasting (Post-Exposure Bake, PEB), development after being exposed Pattern.It should be noted that the thickness of resist film is not particularly limited, it is often preferred that 30~500nm, more preferably 50 ~400nm.

In addition, the light of exposure suitably selects to use according to the photo anti-corrosion agent material used.Usually using wavelength Below 300nm high-energy rays, can specifically be included：248nm, 193nm, 157nm PRK, 3~20nm Grenz ray, electron beam, X-ray etc..

Pattern collapse is inhibited by the basilar memebrane of present embodiment by the corrosion-resisting pattern of above-mentioned method formation.Cause This, by using the basilar memebrane of present embodiment, can obtain finer pattern, resist furthermore it is possible to be reduced to obtain this Corrosion figure case and required light exposure.

Then, mask is made in obtained corrosion-resisting pattern and be etched.As the etching of the basilar memebrane in 2 layer process, Preferably use gas etch.The use of the etching of oxygen is suitable as gas etch.Except oxygen, He, Ar can also be added Deng non-active gas, CO, CO₂、NH₃、SO₂、N₂、NO₂、H₂Gas.Alternatively, it is also possible to only use CO, CO without using oxygen₂、NH₃、 N₂、NO₂、H₂Gas carries out gas etch.In order to which the side wall for the undercutting for prevent pattern sidewalls is protected, especially using the latter's Gas.On the other hand, at the intermediate layer in etching 3 layer process it is also preferred that using gas etch.It is used as gas etch, Ke Yiying With the key element identical key element with illustrating in 2 above-mentioned layer process.The processing in the intermediate layer in particularly 3 layer process is preferably used The gas of freon system, corrosion-resisting pattern is made mask to carry out.Thereafter, intermediate layer pattern can be made as described above Mask, the processing of basilar memebrane is carried out by progress such as oxygen etch.

Herein, in the case where forming inorganic hardmask interlayer film as intermediate layer, the formation such as CVD, ALD is passed through Silicon oxide film, silicon nitride film, silicon oxynitride film (SiON films).As the forming method of nitride film, it is not limited to following, for example may be used To enumerate：Described in Japanese Unexamined Patent Publication 2002-334869 publications (patent document 6), WO2004/066377 (patent document 7) Method.

Photoresist film can be directly formed on such interlayer film, can also be by rotary coating in intermediate layer Organic antireflection film (BARC) is formed on film, and is formed on photoresist film.

As intermediate layer, it is also preferred that using the intermediate layer on polysilsesquioxane basis.By having resist interlayer film There is the effect as antireflection film, so as to have the tendency of effectively suppress reflection.The intermediate layer on polysilsesquioxane basis Specific material is not limited to following, for example, can enumerate：Japanese Unexamined Patent Publication No. 2007-226170 (patent document 8), Japanese Unexamined Patent Publication Material described in No. 2007-226204 (patent document 9).

In addition, the etching of ensuing substrate can also be carried out by conventional method, if for example, substrate is SiO₂、 SiN, then can be carried out based on the etching of freon system gas；If substrate is p-Si, Al, W, it can carry out with chlorine System, the etching that bromine system gas is main body.In the case where being etched with freon system gas to substrate, 2 layers of resist technique Siliceous resist and the siliceous intermediate layers of 3 layer process be stripped while substrate is processed.On the other hand, with chlorine system or bromine It is the stripping that siliceous resist layer or siliceous intermediate layer are additionally carried out in the case that gas is etched to substrate, generally in base Carry out peeling off using the dry ecthing of freon system gas after plate processing.

The basilar memebrane of present embodiment has the excellent feature of the elching resistant of these substrates.

It should be noted that substrate can suitably select, using known substrate, to be not particularly limited, can enumerate：Si、 α-Si、p-Si、SiO₂, SiN, SiON, W, TiN, Al etc..In addition, substrate can be to have to be processed on base material (supporter) The layered product of film (processed substrate).As such machined membrane, Si, SiO can be enumerated₂、SiON、SiN、p-Si、α-Si、 The various Low-k films such as W, W-Si, Al, Cu, Al-Si and its barrier film etc., usually using different from base material (supporter) material Material.It should be noted that to being not particularly limited as the substrate of processing object or the thickness of machined membrane, it is often preferred that 50~10000nm or so, more preferably 75~5000nm.

[purification process of compound or resin]

The purification process of compound or resin in present embodiment includes making solution (A) contact to enter with acidic aqueous solution The process of row extraction, the solution (A) is contained：The organic solvent and the compound of present embodiment not mixed arbitrarily with water Or the resin of present embodiment.Constitute, therefore, using the purification process of present embodiment, can reduce at this as described above The content for the various metals that can be included in the form of impurity in the compound of embodiment or the resin of present embodiment.

More specifically, in present embodiment, it can be dissolved in aforesaid compound or aforementioned resin and not mixed arbitrarily with water The organic solvent of sum, and then make the solution contact with acidic aqueous solution to carry out extraction processing.Thus, make contained in solution (A) Metal ingredient migrated to aqueous phase after, by organic phase and aqueous phase separation, tenor is reduced, this embodiment party can be obtained The compound of formula or the resin of present embodiment.

The compound of present embodiment or the resin of present embodiment can individually be supplied to above-mentioned purifying, can also be by 2 kinds It is mixed above and be supplied to above-mentioned purifying.In addition, the compound of present embodiment or the resin of present embodiment can also be containing each Plant surfactant, various crosslinking agents, various acid agents, various stabilizers etc..

As the organic solvent not mixed arbitrarily with water used in present embodiment, it is not particularly limited, preferably room Organic solvent under temperature to the solubility of water less than 30%, more preferably less than 20%, especially preferably less than 10% can be safe Ground is used for the organic solvent of semiconductor fabrication process.For the amount of the organic solvent used, relative to previously described formula (1) institute used The compound shown or the tree as obtained from the compound shown in previously described formula (1) with the reaction of the compound with crosslinking reactivity Fat, usually using 1~100 mass times or so.

As the concrete example of used solvent, it is not limited to following, can enumerates：The ethers such as diethyl ether, diisopropyl ether, The esters such as ethyl acetate, n-butyl acetate, isoamyl acetate, MEK, methyl iso-butyl ketone (MIBK), ethyl isobutylo ketone, cyclohexanone, The ketones such as cyclopentanone, 2-HEPTANONE, 2 pentanone, ethylene glycol monoethylether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether Aliphatic hydrocarbon, the first such as glycol ethers acetate esters, n-hexane, the normal heptanes such as acetic acid esters (PGMEA), propylene glycol monoethyl ether acetate Halogenated hydrocarbons such as benzene, dimethylbenzene etc. are aromatic hydrocarbon, dichloromethane, chloroform etc..Wherein, preferably toluene, 2-HEPTANONE, cyclohexanone, Cyclopentanone, methyl iso-butyl ketone (MIBK), propylene glycol methyl ether acetate, ethyl acetate etc., more preferably methyl iso-butyl ketone (MIBK), acetic acid second Ester, cyclohexanone, propylene glycol methyl ether acetate, still more preferably methyl iso-butyl ketone (MIBK), ethyl acetate.From present embodiment The aspect that saturation solubility is higher, boiling point is relatively low of the resin of compound or present embodiment is set out, methyl iso-butyl ketone (MIBK), acetic acid Ethyl ester etc. can reduce industrial distillation and remove the situation of solvent, by drying the load in the process being removed.

These solvents can be used individually, can also be mixed with two or more in addition.

, can be from making the organic and inorganic system of public domain as the acid aqueous solution used in present embodiment Suitably selected among the aqueous solution obtained from compound is dissolved in water.It is not limited to following, for example, can enumerates：Make hydrochloric acid, sulfuric acid, The inorganic acid solutions such as nitric acid, phosphoric acid the aqueous solution or make acetic acid, propionic acid, oxalic acid, malonic acid, butanedioic acid, richness obtained from water The organic acids such as horse acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-methyl benzenesulfonic acid, trifluoroacetic acid are dissolved in water Obtained from the aqueous solution.These acid aqueous solution can be used individually, and two or more can also be applied in combination in addition. In these acid aqueous solution, more than a kind be preferably selected from the group that is made up of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid it is inorganic Aqueous acid or, selected from by acetic acid, propionic acid, oxalic acid, malonic acid, butanedioic acid, fumaric acid, maleic acid, tartaric acid, citric acid, first More than a kind of aqueous solutions of organic acids in the group that sulfonic acid, phenolsulfonic acid, p-methyl benzenesulfonic acid and trifluoroacetic acid are constituted, more preferably sulphur The aqueous solution of the carboxylic acid such as sour, nitric acid and acetic acid, oxalic acid, tartaric acid, citric acid, further preferred sulfuric acid, oxalic acid, tartaric acid, lemon The aqueous solution of the aqueous solution, still more preferably oxalic acid of lemon acid.Due to the polybasic carboxylic acids such as oxalic acid, tartaric acid, citric acid and metal Ion is coordinated, and the effect of chelating agent is produced, it can be considered that being to tend to more effectively remove the thing of the tendency of metal Matter.In addition, purpose in the embodiment, water used herein preferably uses the few water of tenor, such as ion exchange Water etc..

The pH of the acid aqueous solution to being used in present embodiment is not particularly limited, it is contemplated that to present embodiment The influence of the resin of compound or present embodiment, the acidity of the preferred pair aqueous solution is adjusted.Usual pH scope is 0~5 Left and right, preferably pH are 0~3 or so.

The consumption of the acid aqueous solution to being used in present embodiment is not particularly limited, and is used to remove metal from reducing Extraction times viewpoint and from the viewpoint of ensuring operability in view of whole amount of liquid, the preferred pair consumption is adjusted Section.From the above point of view, the consumption of the aqueous solution be commonly angled relative to be dissolved in the present embodiment of organic solvent compound or The solution of the resin of present embodiment is 10~200 mass %, is preferably 20~100 mass %.

In present embodiment, by making acidic aqueous solution as described above be contacted with solution, the solution contains：This implementation The compound of mode or the resin of present embodiment and the organic solvent not mixed arbitrarily with water, so as to extracting metals Composition.

In present embodiment, solution (A) is preferably also containing the organic solvent arbitrarily mixed with water.Containing arbitrarily being mixed with water Organic solvent when, have following tendency：The input amount of the compound of present embodiment or the resin of present embodiment can be increased, And point fluidity is improved, and can be purified with high kettle efficiency.Adding the method for the organic solvent arbitrarily mixed with water does not have It is particularly limited to.It for example can be the method being previously added into the solution comprising organic solvent, be previously added to water or acid water Method in solution, the method for making the solution comprising organic solvent be added after being contacted with water or acidic aqueous solution,.Its In, workability, the easiness aspect of input amount management from operation are preferably previously added to the solution comprising organic solvent In method.

As the organic solvent arbitrarily mixed with water used in present embodiment, it is not particularly limited, preferred semiconductor It is capable of the organic solvent of safety applications in manufacturing process.As long as the amount of the organic solvent arbitrarily mixed with water used is solution Scope separated from the water is just not particularly limited, relative to the compound or the resin of present embodiment of present embodiment, leads to Often using 0.1~100 mass times or so.

As the concrete example of the solvent arbitrarily mixed with water used in present embodiment, following, Ke Yiju is not limited to Go out：The ketone such as alcohols, acetone, the 1-METHYLPYRROLIDONEs such as ethers, methanol, ethanol, the isopropanols such as tetrahydrofuran, 1,3- dioxolanes The fat such as the glycol ethers such as class, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), dihydroxypropane single-ether Race's hydro carbons.Wherein, preferably 1-METHYLPYRROLIDONE, propylene glycol monomethyl ether etc., more preferably 1-METHYLPYRROLIDONE, propane diols list first Ether.These solvents can be used individually, can also be mixed two or more and be used.

In present embodiment, when solution (A) is contacted with acidic aqueous solution, i.e., carry out extraction processing when temperature be usually 20~90 DEG C, preferably 30~80 DEG C of scope.Extracting operation is not particularly limited, for example, making it fully mix by stirring etc. Stood after conjunction, so as to be extracted.Thus, the resin of the compound comprising present embodiment or present embodiment and organic Contained metal ingredient is migrated to aqueous phase in the solution of solvent.In addition, by this operation, the acid degree of solution is reduced, can pressed down The compound of present embodiment processed or the resin of present embodiment it is rotten.

Mixed solution is separated into the resin of the compound comprising present embodiment or present embodiment and had by standing The solution and aqueous phase of machine solvent, therefore utilize the compound or present embodiment of the packet receiving containing present embodiment back and forth such as decantation The solution of resin and organic solvent.The time of standing is not particularly limited, from preferably to the solution comprising organic solvent From the viewpoint of being separated with aqueous phase, the time of the standing is preferably adjusted.The time generally stood is more than 1 minute, preferably For more than 10 minutes, more preferably more than 30 minutes.In addition, extraction processing can be only 1 time, but be repeated several times mixed, Stand, the such operation of separation is also effective.

In present embodiment, preferably：Extraction processing is carried out using the process for making solution (A) be contacted with acidic aqueous solution Afterwards, in addition to carry out using water extraction processing process.Namely it is preferred that：Above-mentioned extraction is being carried out using the acid aqueous solution Take after processing, by from the aqueous solution extract, reclaim the compound comprising present embodiment or present embodiment resin with And the solution of organic solvent is further for the extraction processing using water.The extraction processing of above-mentioned utilization water is not particularly limited, Such as can by using stirring be sufficiently mixed after stand and carry out.Because the solution obtained after the standing is separated into comprising this The solution and aqueous phase of the compound of embodiment or the resin of present embodiment and organic solvent, thus by be decanted etc. come Reclaim the compound of present embodiment or the resin and the solution of organic solvent of present embodiment.

In addition, according to the purpose of present embodiment, water used herein is preferably the few water of tenor, the friendship of such as ion Change water etc..Extraction processing can be carried out only 1 time, but it is also effective that mixing, which is repeated several times, stands, separate such operation.Separately Outside, both conditions such as use ratio, temperature, time in extraction processing are not particularly limited, can with before with acidity The contact disposition of the aqueous solution is identical.

The compound comprising present embodiment or the resin of present embodiment obtained in this way for that can be mixed into And the moisture in the solution of organic solvent, it can be readily removable by implementing the operation such as vacuum distillation.In addition, according to need Organic solvent can be added and the concentration of the compound of present embodiment or the resin of present embodiment is adjusted to arbitrary Concentration.

For from the molten of the obtained compound comprising present embodiment or the resin of present embodiment and organic solvent The method that the compound of present embodiment or the resin of present embodiment are separated in liquid, is not particularly limited, for example, can pass through Method known to removal, the separation based on reprecipitation and combinations thereof etc. is depressurized to carry out.It can carry out as needed dense Contract and handled known to operation, filter operation, centrifugation operation, drying process etc..

Embodiment

Hereinafter, present embodiment is illustrated in more detail by synthesis example and embodiment, but present embodiment not by Any restriction of these examples.

(concentration of carbon and oxygen concentration)

Concentration of carbon and oxygen concentration (quality %) are determined by organic element analysis.

Device：CHN CORDER MT-6 (Yanaco Co., Ltd. system)

(molecular weight)

Analyzed, be measured using Agilent company systems Agilent5975/6890N by GC-MS.Or, pass through LC- MS is analyzed, and is measured using Water company system Acquity UPLC/MALDI-Synapt HDMS.

(molecular weight determination)

Analyzed by Field desorption mass spectra analytic approach (FD-MS), obtain molecular weight.

(polystyrene conversion molecular weight)

Weight average molecular weight (Mw), number that polystyrene converts is obtained by gel permeation chromatography (GPC) analysis to divide equally Son amount (Mn), and obtain decentralization (Mw/Mn).

Device：Shodex GPC-101 types (Showa Denko K. K's system)

Chromatographic column：KF-80M×3

Eluent：THF 1mL/ minutes

Temperature：40℃

(heat decomposition temperature (Tg))

Using SII NanoTechnology Inc. EXSTAR6000DSC devices, sample about 5mg is put into aluminum non- In sealing container, 500 DEG C are warming up to 10 DEG C/min of programming rate in nitrogen (30mL/ minutes) air-flow.Now, will be There is subtracting least a portion of temperature as heat decomposition temperature (Tg) in baseline, with following benchmark evaluation heat resistance.

Evaluate A：Heat decomposition temperature >=150 DEG C

Evaluate C：Heat decomposition temperature<150℃

(solubility)

At 23 DEG C, compound phase is set to be dissolved for cyclohexanone (CHN) in the way of as 5 mass % solution, afterwards, 30 days are stood at 5 DEG C, with following benchmark evaluation result.

Evaluate A：Visually to confirm no precipitate

Evaluate C：There is precipitate with visual confirmation

(synthesis example 1) BisN-1 synthesis

In possessing the internal volume 1000mL container of mixer, condenser pipe and buret, 2,6- naphthalenediols are put into (Sigma-Aldrich company systems reagent) 16.0g (100mmol), 4- biphenyl aldehyde (Mitsubishi Gas Chemical Co., Ltd's system) 18.2g (100mmol) and methyl iso-butyl ketone (MIBK) 300mL, the sulfuric acid 50mL of addition 95%, reaction solution is stirred 6 hours at 100 DEG C, Reacted.Then, reaction solution is concentrated, adds pure water 500g, separate out reaction product, be cooled to after room temperature, filtered And separate.Make after being dried by the solids being filtrated to get, isolating and purifying using column chromatography is carried out, so as to obtain following formula Shown target compound (BisN-1) 30.5g.

It should be noted that being found that following peak by 400MHz-1H-NMR, it is thus identified that the chemistry knot with following formula Structure.In addition, it is that the signal of the proton according to 3 and 4 is dual to confirm that the position of substitution of 2,6- dihydroxy naphthols, which is 1, 's.

1H-NMR：(d-DMSO, internal standard TMS)

δ (ppm) 9.7 (2H, O-H), 7.2~8.5 (19H, Ph-H), 6.6 (1H, C-H)

(synthetic example 1) BisN-1-CH1 and BisN-1-CH2 synthesis

In possessing the internal volume 1000mL container of mixer, condenser pipe and buret, obtained during addition is foregoing BisN-1 11.7g (25mmol), potassium carbonate 108g (810mmol) and dimethylformamide 200mL, add bromine hexamethylene 250g (1.53mol), reaction solution is stirred 24 hours at 110 DEG C, reacted.Then, reaction solution is concentrated, adds pure water 500g, separates out reaction product, is cooled to after room temperature, is filtered and is separated.Gained solids is filtered, made after its drying, Carry out isolating and purifying using column chromatography, thus obtain target compound (BisN-1-CH1) 2.4g shown in following formula and (BisN-1-CH2)9.6g。

For gained compound, NMR measure is carried out under foregoing condition determination, following peak is as a result found that, it is thus identified that Chemical constitution with following formula.

BisN-1-CH1：δ (ppm) 9.7 (1H, O-H), 7.2~8.5 (19H, Ph-H), 6.6 (1H, C-H), 1.4~4.5 (11H, Cy-H)

Herein, Cy-H is the signal of the proton of cyclohexyl.

BisN-1-CH2：δ (ppm) 7.2~8.5 (19H, Ph-H), 6.6 (1H, C-H), 1.4~4.5 (22H, Cy-H)

Herein, Cy-H is the signal of the proton of cyclohexyl.

Gained BisN-1-CH1 molecular weight is 548.In addition, it is 8.8 matter that concentration of carbon, which is 85.3 mass %, oxygen concentration, Measure %.

Gained BisN-1-CH2 molecular weight is 630.In addition, it is 7.6 matter that concentration of carbon, which is 85.7 mass %, oxygen concentration, Measure %.

(synthetic example 2) BisN-1-PH1 synthesis

In possessing the internal volume 1000mL container of mixer, condenser pipe and buret, obtained during input is foregoing BisN-1 9.3g (20mmol), cesium carbonate 26g (80mmol), cupric iodide 0.8g (4mmol), dimethyl glycine hydrochloride 1.7g (12mmol) and dioxane 80mL, adds benzene iodide 8.2g (40mmol), reaction solution is stirred into 6 at 90 DEG C Hour is reacted.Then, ethyl acetate 500mL is added, reaction product is separated out, is cooled to after room temperature, filtered and divided From.Gained solids is filtered, makes after its drying, isolating and purifying using column chromatography is carried out, so as to obtain shown in following formula Target compound (BisN-1-PH1) 7.2g.

BisN-1-PH1：δ (ppm) 9.2 (1H, O-H), 6.7~7.8 (24H, Ph-H), 5.3 (1H, C-H)

(synthetic example 3) BisN-1-PH2 synthesis

In possessing the internal volume 1000mL container of mixer, condenser pipe and buret, obtained during input is foregoing BisN-1 9.3g (20mmol), cesium carbonate 26g (80mmol), cupric iodide 0.8g (4mmol), dimethyl glycine hydrochloride 1.7g (12mmol) and dioxane 80mL, adds benzene iodide 8.2g (40mmol), reaction solution is stirred into 67 at 90 DEG C Hour is reacted.Then, adding ethyl acetate 500mL separates out reaction product, is cooled to after room temperature, is filtered and divided From.Gained solids is filtered, makes after its drying, isolating and purifying using column chromatography is carried out, so as to obtain shown in following formula Target compound (BisN-1-PH2) 6.8g.

BisN-1-PH2：δ (ppm) 6.8~8.0 (29H, Ph-H), 5.3 (1H, C-H)

It should be noted that gained BisN-1-PH1 molecular weight is 542.In addition, concentration of carbon is 86.3 mass %, oxygen is dense Spend for 8.9 mass %.

Gained BisN-1-PH2 molecular weight is 618.In addition, it is 7.8 matter that concentration of carbon, which is 87.4 mass %, oxygen concentration, Measure %.

(Production Example 1)

In the dismountable internal volume 10L in serpentine condenser, thermometer and stirring vane, bottom four-hole boiling flask In, 1,5- dimethylnaphthalenes 1.09kg (7mol, Mitsubishi Gas Chemical Co., Ltd are put into the four-hole boiling flask in stream of nitrogen gas System), 40 mass % formlinata aquae concentratacs 2.1kg (28mol, Mitsubishi Gas Chemical Co., Ltd's system are calculated as with formaldehyde) and 98 matter Measure % sulfuric acid (Kanto Kagaku K. K.'s system) 0.97mL, make its at ambient pressure, 100 DEG C of following backflow sides react 7 hours.Its Afterwards, as retarder thinner, ethylo benzene (Wako Pure Chemical Industries, Ltd.'s reagent is superfine) 1.8kg is added into reaction solution, it is quiet Postpone the aqueous phase for removing lower floor.And then neutralized and washed, distillation under reduced pressure removes ethylo benzene and unreacted 1,5- bis- Methyl naphthalene, thus obtains the dimethylnaphthalene formaldehyde resin 1.25kg of hazel-color solid.

The molecular weight of obtained dimethylnaphthalene formaldehyde is：Mn：562、Mw：1168、Mw/Mn：2.08.In addition, concentration of carbon is 84.2 mass %, oxygen concentration are 8.3 mass %.

Afterwards, in the four-hole boiling flask of the internal volume 0.5L with serpentine condenser, thermometer and stirring vane, in nitrogen Obtained dimethylnaphthalene formaldehyde resin 100g (0.51mol) is put into the four-hole boiling flask in Production Example 1 under air-flow and to toluene Sulfonic acid 0.05g, is warming up to 190 DEG C and is stirred after heating 2 hours.Thereafter, 1- naphthols 52.0g is further added (0.36mol), and then be warming up to 220 DEG C and it is reacted 2 hours.Neutralized and washed after solvent dilution, gone under reduced pressure Except solvent, modified resin (CR-1) 126.1g of dark brown solid is thus obtained.

Obtained resin (CR-1) is：Mn：885、Mw：2220、Mw/Mn：4.17.In addition, concentration of carbon be 89.1 mass %, Oxygen concentration is 4.5 mass %.

(embodiment 1~4, comparative example 1)

For above-mentioned BisN-1-CH1, BisN-1-CH2, BisN-1-PH1, BisN-1-PH2 and BisN-1, carry out heat-resisting Property experiment and solubility test.Show the result in table 1.

In addition, the photoetching for preparing the composition shown in table 1 respectively substrate film formation material.Then, by these basilar memebrane shapes Into material rotary coating on silicon substrate, afterwards, bakeed 60 seconds and then bakeed 120 seconds with 400 DEG C with 240 DEG C, film is made respectively Thick 200nm basilar memebrane.For acid agent, crosslinking agent and organic solvent, following material is used.

Acid agent：The fluoromethane sulfonate of Midori Kagaku Co., Ltd.s di-t-butyl diphenyl iodine nine (in table, It is denoted as " DTDPI ")

Crosslinking agent：SANWA CHEMICAL Co., Ltd.s NIKALAC MX270 (in table, being designated as " NIKALAC ")

Organic solvent：Cyclohexanone (in table, is denoted as " CHN ")

[etching test]

And then, it is following it is shown under conditions of be etched experiment, evaluate elching resistant.Evaluation result is shown in table 1.

Etaching device：SAMCO International Inc. RIE-10NR

Output：50W

Pressure：20Pa

Time：2min

Etching gas

Ar gas flows：CF₄Gas flow：O₂Gas flow=50：5：5(sccm)

[evaluation of elching resistant]

The evaluation of elching resistant is carried out according to the following steps.

First, the compound used in embodiment 1 is replaced with novolaks (Qun Rong KCC PSM4357) (BisN-1-CH1) basilar memebrane of novolaks, in addition, is made under conditions of similarly to Example 1.Then, it is somebody's turn to do The above-mentioned etching test of the basilar memebrane of novolaks, determines etch-rate now.

Then, the etching test of the basilar memebrane of embodiment 1 and comparative example 1 is similarly carried out, etch-rate now is determined.

Then, on the basis of the etch-rate of the basilar memebrane of novolaks, elching resistant is evaluated according to following metewand. Show the result in table 1.

<Metewand ＞

A：Compared with the basilar memebrane of novolaks, etch-rate is less than -10%

B：Compared with the basilar memebrane of novolaks, etch-rate is -10%~+5%

C：Compared with the basilar memebrane of novolaks, etch-rate exceedes+5%

Then, BisN-1-CH1, BisN-1-CH2, BisN-1-PH1, BisN-1-PH2, BisN-1 reality will be included respectively Example 1~4, the photoetching of comparative example 1 are applied with each solution coating of substrate film formation material in thickness 300nm SiO₂On substrate, Bakee 60 seconds, and then bakeed 120 seconds at 400 DEG C at 240 DEG C, thus form thickness 80nm basilar memebrane respectively.ArF is used anti- Erosion agent solution is coated on the basilar memebrane, is bakeed 60 seconds at 130 DEG C, is consequently formed thickness 150nm photoresist layer.Need It is noted that as ArF Resist Solutions, using the solution for being compounded following material and preparing：The compound of following formula (11)： 5 mass parts, the fluoromethane sulfonate of triphenylsulfonium nine：1 mass parts, tri-n-butylamine：2 mass parts and PGMEA：92 mass parts.

The compound of following formula (11) is obtained as follows：Make 2- methyl -2- methacryloxyadamantanes 4.15g, methyl Acryloxy-gamma-butyrolacton 3.00g, 3- hydroxyl -1- adamantyl methacrylates 2.08g, azodiisobutyronitrile 0.38g is dissolved in tetrahydrofuran 80mL, keeps reaction temperature to be 63 DEG C in a nitrogen atmosphere, it is polymerize 22 hours, then will Reaction solution is added dropwise in 400mL n-hexane, purifies generation hardening of resin, filters the white powder of generation, under reduced pressure It is dried overnight with 40 DEG C, so as to obtain.

(in formula (11), 40,40,20 represent the ratio of each construction unit, and not represent block copolymer.)

Then, using electron beam lithography system (ELIONIX Inc. systems；ELS-7500,50keV) to photoresist layer Exposure is masked, 90 seconds (PEB) is bakeed at 115 DEG C, is entered with 2.38 mass % TMAHs (TMAH) aqueous solution Row develops for 60 seconds, thus obtains the corrosion-resisting pattern of eurymeric.

Will observation gained 55nmL/S (1：1) with 80nmL/S (1：1) shape of corrosion-resisting pattern and the result of defect are shown in Table 1.

(comparative example 2)

Using CR-1, in addition, carried out in the same manner as embodiment 1~4, comparative example 1, prepare substrate film formation material, Rotary coating afterwards, is bakeed 60 seconds with 240 DEG C and then bakeed 120 seconds with 400 DEG C, make thickness 200nm's on silicon substrate Basilar memebrane.Afterwards, elching resistant is evaluated.Show the result in table 1.

(comparative example 3)

Without the formation of basilar memebrane, in addition, carried out in the same manner as embodiment 1~4, comparative example 1, by photoresist Oxidant layer is formed directly into SiO₂On substrate, the corrosion-resisting pattern of eurymeric is obtained.Evaluation result is shown in table 1.

[table 1]

Clearly confirmed by table 1, use the compound i.e. BisN-1-CH1 embodiment for the feature for meeting present embodiment 1st, using BisN-1-CH2 embodiment 2, the embodiment 3 using BisN-1-PH1 and using BisN-1-PH2 embodiment 4 in, It is good in terms of heat resistance, solubility and elching resistant.On the other hand, using in polyphenolic substance BisN-1 comparative example 1, Heat resistance and elching resistant are good, but solubility is bad.In addition, using CR-1 (phenol-modified dimethylnaphthalene formaldehyde resins (CR-1) in comparative example 2, elching resistant is bad.

Confirm in addition, in embodiment 1~4, the corrosion-resisting pattern shape after development is good, also no defects.On the other hand, Confirm, in comparative example 1, the corrosion-resisting pattern shape defect after development, defect is also more.Speculate this is because, being used in comparative example 1 BisN-1 for coating solvent be low-solubility.

And then confirm, compared with the comparative example 3 of formation of the embodiment 1~4 with eliminating basilar memebrane, resolution ratio and sensitivity It is significantly excellent.

According to the difference of the corrosion-resisting pattern shape after development, show the photoetching of embodiment 1~4 with substrate film formation material with The adaptation of anticorrosive additive material is good.

(embodiment 5)

By the photoetching used in embodiment 1 with the solution coating of substrate film formation material in thickness 300nm SiO₂Substrate On, bakeed 60 seconds and then bakeed 120 seconds with 400 DEG C with 240 DEG C, be consequently formed thickness 80nm basilar memebrane.On the basilar memebrane Siliceous intermediate layer material is coated with, is bakeed 60 seconds with 200 DEG C, is consequently formed thickness 35nm interlayer film.And then, in the intermediate layer Foregoing ArF Resist Solutions are coated with film, is bakeed 60 seconds with 130 DEG C, is consequently formed thickness 150nm photoresist layer. It should be noted that as siliceous intermediate layer material, using Japanese Unexamined Patent Publication 2007-226170 publications<Described in the ＞ of synthesis example 1 Silicon atoms polymer.

Then, using electron beam lithography system (ELIONIX Inc. systems；ELS-7500,50keV) to photoresist layer Exposure is masked, 90 seconds (PEB) is bakeed at 115 DEG C, is entered with 2.38 mass % TMAHs (TMAH) aqueous solution Row develops for 60 seconds, thus obtains 55nmL/S (1：1) corrosion-resisting pattern of eurymeric.

Afterwards, using SAMCO International Inc. RIE-10NR, using gained corrosion-resisting pattern as mask, carry out The dry ecthing processing of siliceous interlayer film (SOG), then, is carried out successively：Using the siliceous interlayer film pattern of gained as the base of mask The dry ecthing of counterdie is processed and using gained substrate film figure as the SiO of mask₂The dry ecthing processing of film.

Each etching condition is as shown in following.

Etching condition of the corrosion-resisting pattern to resist interlayer film

Output：50W

Pressure：20Pa

Time：1min

Etching gas

Ar gas flows：CF₄Gas flow：O₂Gas flow=50：8：2(sccm)

The etching condition of film figure confrontation erosion agent basilar memebrane in the middle of resist

Output：50W

Pressure：20Pa

Time：2min

Etching gas

Ar gas flows：CF₄Gas flow：O₂Gas flow=50：5：5(sccm)

Resist-based counterdie pattern is to SiO₂The etching condition of film

Output：50W

Pressure：20Pa

Time：2min

Etching gas

Ar gas flows：C₅F₁₂Gas flow：C₂F₆Gas flow：O₂Gas flow

=50：4：3：1(sccm)

The implementation obtained as described above using electron microscope (S-4800) observation of Hitachi Co., Ltd Pattern section (the SiO after etching of example 5₂The shape of film).As a result, for the substrate using the feature for meeting present embodiment The embodiment 5 of film, the SiO after etching in the processing of multilayer resist₂Film is shaped as rectangle, does not also confirm defect, really Think good.

As described above, the present invention is not limited to the above-described embodiment and examples, in the range of its purport is not departed from, Can also suitably it be changed.

The application, will based on Japanese patent application filed in 25 days December in 2014 (Japanese Patent Application 2014-262564) Its content is introduced so far as reference.

Industrial applicability

The present invention compound and resin concentration of carbon it is higher, oxygen concentration is relatively low, heat resistance is higher, solvent solubility compared with Height, can apply wet processing, therefore, can widely and effectively be utilized in the various uses for require these performances.Therefore, originally Invention for example electrically can be bonded with insulating materials, resist resin, semiconductor potting resin, use in printed circuit board Agent, be installed on electric equipment electronic equipment industry equipment etc. it is electric with plywood, be installed on electric equipment electronic equipment The matrix resin of the prepreg of industrial equipment etc., lamination plywood material, fiber-reinforced plastic resin, liquid crystal display panel Sealing resin, coating, various smears, bonding agent, the smears of semiconductor, resist resin, the base of semiconductor Counterdie formation is widely and effectively utilized with resin etc..Particularly, the present invention can be against corrosion in photoetching basilar memebrane and multilayer Agent is particularly effectively utilized with the field of basilar memebrane.

Claims

1. the compound shown in a kind of following formula (1),

In formula (1), X separately represents oxygen atom or sulphur atom or for without crosslinking, R¹For singly-bound or the 2n of carbon number 1~30 Valency group, the group optionally has the aryl of alicyclic type hydrocarbon, double bond, hetero atom or carbon number 6~30, R²It is separately carbon The straight-chain of number 1~10, the alkyl of branched or ring-type, the aryl of carbon number 6~10, the alkenyl of carbon number 2~10, carbon number 1~ 30 alkoxy, the aryloxy group or hydroxyl of carbon number 6~30, herein, R²In at least one be carbon number 1~30 alkoxy or carbon The aryloxy group of number 6~30, m is separately 1~6 integer, the integer that p is separately 0 or 1, n are 1~4.

2. compound according to claim 1, wherein, the compound shown in the formula (1) is shown in following formula (1A-2) Compound,

In formula (1A-2), R¹With p and the identical meanings, R⁶With the R of explanation in the formula (1)²For identical meanings, m⁶Independently Ground is 1~3 integer.

3. compound according to claim 1, wherein, the compound shown in the formula (1) is shown in following formula (1B-2) Compound,

In formula (1B-2), R¹With p and foregoing same, R⁶With the R of explanation in the formula (1)²For identical meanings, m⁶It is separately 1~3 integer.

4. compound according to claim 2, wherein, the compound shown in the formula (1A-2) is following formula (BisN-1- CH1) or the compound shown in following formula (BisN-1-CH2),

5. compound according to claim 2, wherein, the compound shown in the formula (1A-2) is following formula (BisN-1- PH1) or the compound shown in following formula (BisN-1-PH2),

6. a kind of resin, its be using compound according to any one of claims 1 to 5 as obtained from monomer.

7. resin according to claim 6, it is with having by compound according to any one of claims 1 to 5 Obtained from the compound reaction of crosslinking reactivity.

8. resin according to claim 7, wherein, the compound with crosslinking reactivity is selected from by aldehyde, ketone, carboxylic Acid, acid halide, halogen contained compound, amino-compound, imino-compound, isocyanates and the compound containing unsaturated alkyl It is at least one kind of in the group of composition.

9. resin according to claim 6 is comprising structure shown in following formula (2),

In formula (2), X separately represents oxygen atom or sulphur atom or for without crosslinking, R¹For singly-bound or the 2n of carbon number 1~30 Valency group, the group optionally has the aryl of alicyclic type hydrocarbon, double bond, hetero atom or carbon number 6~30, R²It is separately carbon The straight-chain of number 1~10, the alkyl of branched or ring-type, the aryl of carbon number 6~10, the alkenyl of carbon number 2~10, carbon number 1~ 30 alkoxy, the aryloxy group or hydroxyl of carbon number 6~30, herein, R²In at least one be carbon number 1~30 alkoxy or carbon The aryloxy group of number 6~30, R³It is separately the straight-chain or the alkylidene of branched of singly-bound or carbon number 1~20, m²Respectively It independently is 1~5 integer, the integer that p is separately 0 or 1, n are 1~4.

10. resin according to claim 9, wherein, the resin with the structure shown in the formula (2) is with following formula The resin of structure shown in (2A),

In formula (2A), R¹、R²、R³、m², p and n with it is foregoing same.

11. resin according to claim 9, wherein, the resin with the structure shown in the formula (2) is with following formula The resin of structure shown in (2B),

In formula (2B), R¹、R²、R³、m², p and n with it is foregoing same.

12. a kind of photoetching substrate film formation material, it contains：Compound according to any one of claims 1 to 5 and/or Resin any one of claim 6~11.

13. photoetching according to claim 12 substrate film formation material, wherein, also contain organic solvent.

14. the substrate film formation material of the photoetching according to claim 12 or 13, wherein, also contain acid agent.

15. the substrate film formation material of the photoetching according to any one of claim 12~14, wherein, also containing crosslinking Agent.

16. a kind of photoetching basilar memebrane, it is with basilar memebrane to form material as the photoetching any one of claim 12~15 What material was formed.

17. a kind of corrosion-resisting pattern forming method, it possesses following process：

Process (A-1), the photoetching substrate film formation material any one of usage right requirement 12~15, the shape on substrate Into basilar memebrane；

Process (A-2), forms at least 1 layer of photoresist layer on the basilar memebrane；With,

Process (A-3), after the process (A-2), to the predetermined region illumination radiation line of the photoresist layer, is shown Shadow.

18. a kind of circuit pattern forming method, it possesses following process：

Process (B-1), the photoetching substrate film formation material any one of usage right requirement 12~15, the shape on substrate Into basilar memebrane；

Process (B-2), using the resist interlayer film material containing silicon atom, interlayer film is formed on the basilar memebrane；

Process (B-3), forms at least 1 layer of photoresist layer on the interlayer film；

Process (B-4), after the process (B-3), to the predetermined region illumination radiation line of the photoresist layer, is shown Shadow and form corrosion-resisting pattern；With,

Process (B-5), after the process (B-4), using the corrosion-resisting pattern as mask, is etched to the interlayer film, Using gained interlayer film pattern as etching mask, the basilar memebrane is etched, using gained substrate film figure as etching mask, Substrate is etched, so as to form pattern on substrate.

19. a kind of purification process, it includes the process for making solution (A) contact to be extracted with acidic aqueous solution, the solution (A) contain：The organic solvent not mixed arbitrarily with water and compound according to any one of claims 1 to 5 or right will Seek the resin any one of 6~11.